Studies in Chemical Physics

Advanced Molecular
Quantum Mechanics
An Introduction to Relativistic
Quantum Mechanics and the
Quantum Theory of Radiation -

R. E. Moss
This book contains a lucid account of the
theoretical physics that is necessary for
the appreciation of many of the recent
advances in chemical physics.
Following a summary of vector methods,
classical mechanics and special relativity
are introduced and used to develop
electromagnetic theory. With this back-
ground the Dirac equation for the electron
is considered in detail, this theory
leading naturally to the concept of elec-
tron spin. The extension to many electrons
is then discussed, the end product being a
Hamiltonian containing all the terms of
chemical interest. Finally, the classical
theory of electromagnetic radiation is
quantized and it is shown how quantum
field theory may be used to describe the
interaction of radiation with matter.
The level at which this work is written
should make it particularly suitable for
graduate chemists and chemical physi-
cists. Only the quantum mechanics and
mathematics normally covered in under-
graduate chemistry courses are assumed
and, even so, the pertinent parts are sum-
marized early in the book.

The Author
Richard Moss carried out research in the |
University of Cambridge and at Columbia »

University, New York, before taking up *

his present position at Southampton in .6 ‘
1967. His main research interest is in the () '
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STUDIES IN CHEMICAL PHYSICS

General Editor
A. D. Buckingham, Professor of Chemistry, University of Cambridge

Series Foreword
The field of science known as ‘Chemical Physics’ has
greatly expanded in recent years. It is an essential part of
both physics and chemistry and now impinges on biology,
crystallography, the science of materials and even on
astronomy. The aim of this series is to present short,
authoritative and readable books on different topics in
chemical physics at a level that is appreciated by the non-
specialist and yet is of prime interest to the expert—in fact,
the type of book that we all welcome and enjoy.
I was grateful to be given the opportunity to help plan
this series, and warmly thank the authors and publishers
whose efforts have brought it into being.

A. D. Buckingham,
University Chemical Laboratory,
Cambridge, U.K.

Other titles in the series

Electronic Transitions and the High Pressure Chemistry
and Physics of Solids, H. G. Drickamer and C. W. Frank
Chemical Applications of Molecular Beam Scattering,
M. A. D. Fluendy and K. P. Lawley
Advanced Molecular
Quantum Mechanics
An Introduction to Relativistic Quantum
Mechanics and the Quantum Theory of
Radiation

R. E. MOSS
Lecturer in Chemistry
University of Southampton

Gh
CHAPMAN AND HALL: LONDON
First published 1973
by Chapman and Hall Ltd
11 New Fetter Lane, London EC4P 4EE

© 1973 R. E. Moss

Set by E. W. C. Wilkins Ltd, London N12 0EH

and printed in Great Britain by
Redwood Press Limited, Trowbridge, Wiltshire

SBN 412 10490 3

All rights reserved. No part of this book may be
reprinted, or reproduced or utilized in any form
or by any electronic, mechanical or other means,
now known or hereafter invented, including photo-
copying and recording, or in any information
storage and retrieval system, without permission
in writing from the Publisher.

Distributed in the U.S.A.

by Halsted Press, a Division
of John Wiley & Sons, Inc.
New York
LO SHIRLEY
AND JONATHAN
 Preface

This book is primarily intended for graduate chemists and chemical physicists.
Indeed, it is based on a graduate course that I give in the Chemistry Depart-
ment of Southampton University.
Nowadays undergraduate chemistry courses usually include an introduction
to quantum mechanics with particular reference to molecular properties and
there are a number of excellent textbooks aimed specifically at undergraduate
chemists. In valence theory and molecular spectroscopy physical concepts are
often encountered that are normally taken on trust. For example, electron
spin and the anomalous magnetic moment of the electron are usually accepted
as postulates, although they are well understood by physicists. In addition, the
advent of new techniques has led to experimental situations that can only be
accounted for adequately by relatively sophisticated physical theory. Relativis-
tic corrections to molecular orbital energies are needed to explain X-ray photo-
electron spectra, while the use of lasers can give rise to multiphoton transitions,
which are not easy to understand using the classical theory of radiation. Of
course, the relevant equations may be extracted from the literature, but, if the
underlying physicsisnot understood, this is a practice that is at best dissatisfy-
ing and at worst dangerous. One instance where great care must be taken is in
the use of spectroscopically determined parameters to test the accuracy of elec-
tronic wave functions. The practice of employing classical analogies to add
small terms to the molecular Hamiltonian, as and when they are needed to ex-
plain new phenomena, is no longer satisfactory. It is necessary to start with as
complete a molecular Hamiltonian as possible to make sure that important
contributions to spectroscopic parameters are not omitted.
However, the physics literature that deals with such topics as relativistic
1X
x Preface

quantum mechanics and the quantum theory of electromagnetic radiation

usually assumes a broad physical background that can only be acquired by
reading a number of physics texts. In addition, the pertinent knowledge is
often embedded in a considerable amount of information that is not directly
relevant to molecular physics. The aim of this book is, therefore, to present
sufficient theoretical physics that the theory needed to understand some of
the recent developments in molecular physics may be better appreciated.
Only the quantum mechanics and mathematics that, in my experience, is
usually covered in undergraduate chemistry courses is assumed. Even so, the
relevant parts are summarized in the early chapters, although vector algebra
is considered in some detail, since there are a number of useful sophistications
that do not appear to be covered in the usual texts. Classical mechanics and
special relativity are then introduced with particular reference to a system of
particles and this theory is used to develop electromagnetic theory in such a
way that no knowledge of these subjects is necessary beyond that taught in
schools. With this background the Dirac equation for the electron is considered
in detail; this theory leads naturally to the concept of electron spin and the
correct value for the spin magnetic dipole moment of the electron. The exten-
sion to many electrons and to molecules is then discussed, the end product
being a Hamiltonian containing all the terms of (chemical) interest. Finally,
the classical theory of electromagnetic fields is quantized and it is shown how
quantum field theory may be used to describe the interaction of radiation with
matter. This is but a brief review of the topics covered, but reference to the list
of contents may be made fora more detailed summary.
I do not pretend that the theory described in this book is entirely adequate
to account for all molecular properties. There are, for example, radiative cor-
rections that can only be discussed satisfactorily in terms of quantum electrody-
namics,a subject that is beyond the scope of this book. Nevertheless, an attempt
is made to give a qualitative description of the processes responsible for such
phenomena as the Lamb shift and the radiative correction to the g factor of
the electron.
In a way the subject matter reflects my own interests, since it represents
what I have found necessary to learn, since graduating as a chemist, in order
to pursue my current research interest in high resolution molecular spectros-
copy. There is another personal stamp on this book, since I have a dislike for
appendices and these have been kept to a minimum. The appendix containing a
summary of the useful vector relations derived in Chapter 2 requires no com-
ment. Of the other two, one is a review of the SI system of units, which is
used throughout the book. For those who, despite international agreement,
still prefer to use the mixed (or Gaussian) system, the transition to the SI
Preface xi

system is not trivial. However, no problems should be encountered here, since

electromagnetism, where the main difficulties occur, is developed from first
principles and since tables for the conversion of units and equations are given.
In the remaining appendix a general bibliography is presented; this comprises
a list of the books that are referred to most frequently in the bibliographies at
the ends of the individual chapters. I have made no attempt to provide a com-
plete bibliography and indeed this would be an almost impossible task. The
sources that are cited are those that I have found useful; where appropriate I
have given a brief description of the material covered by the individual refer-
ences. Anyone wishing to consult other sources can always find more refer-
ences in the articles and books that are mentioned in the bibliographies.
It will be apparent that no problems as such are given, but the reader will
often find results quoted, the verification of which provides ample material for
exercises. This is not intended as a textbook, its purpose is to provide suffic-
ient background that the more recent research literature may be approached
with confidence.
Finally, I must thank a number of people for their part in the realization
of this book. Professor A. Carrington first turned my attention to relativistic
effects and Professor A. D. Buckingham suggested the inclusion of the quan-
tum theory of radiation. I am also grateful to these and other colleagues, in
particular DrJ.M. Brown, Dr B. J. Howard, Dr I. J. Ketley and Mr A. J. Perry,
for reading all or parts of the manuscript and helping to remove inaccuracies.
Needless to say the remaining errors are my responsibility alone and I will
appreciate them being pointed out to me. Thanks are also due to Mrs Jean
Gordon and Mrs Christine Croucher, who between them expertly typed the
bulk of the manuscript.
Richard E. Moss

Southampton
July, 1972
Contents

Preface page ix

Non-relativistic Quantum Mechanics

Formal quantum mechanics
The Schrodinger equation
Heisenberg’s uncertainty principle and related topics
Angular momentum
Electron spin
The need for a relativistic theory
Bibliography —WN
NOK
OD
We

Vector and Matrix Algebra jos,Ww

Vectors and vector multiplication

The repeated subscript convention for summation
The Kronecker delta 6;;
The €;;, notation
The €;;,, sum rules
Examples I
The vector operator V
The gradient
The divergence
The curl
Examples II
Second derivatives in vector calculus
The Dirac delta function Oy
=)
SO)
hoy
(OO
fs
—Oir
NOMOO
1
ew!
SI
RO
TILE
SY
[SITE
Mas
ee
laa
St
Contents Xili

2.14 Matrices and determinants: a summary page 33

25 Vectors in four dimensions 36
Bibliography 36

Classical Mechanics 37
Inertial frames and Galileo’s relativity principle eH)
The principle of least action 38
Lagrange’s equations of motion 32
The Lagrangian for a system of particles 41
Constants of motion 43
The Hamiltonian 46
Bibliography 47

Special Relativity 48
Einstein’s principle of relativity 48
The interval 50
The Lorentz transformation 51
Contraction, dilation and paradoxes 54
The transformation of velocities 56
The relativistic mechanics of a free particle 57.
Four-vectors 60
Bibliography 62

The Interaction of Charged Particles with Electromagnetic Fields 63

Units 63
The electromagnetic potentials 64
The field vectors 67
The Lorentz transformation of electric and magnetic fields 68
Gauge transformations 70
Maxwell’s equations ce
The potentials and fields due to a stationary charge ie
The potentials due to a moving charge 76
The interaction of two charged particles 79
The Thomas precession 81
Bibliography 84

The Classical Theory of Electromagnetic Fields 85

6.1 Continuous mechanical systems 85

6.2 The Lagrangian density for an electromagnetic field 90
6.3 The current four-vector 92
 Contents

The second pair of Maxwell’s equations page 93

Electromagnetic waves 95
Solution of the wave equation for free space 97
The characteristic vibrations of an electromagnetic field 100
Bibliography 103

Relativistic Wave Equations 104

Quantization of classical equations 104
Gauge invariance of quantum mechanical equations 107
The Klein-Gordon equation 108
Bibliography 110

The Dirac Equation 111

The Dirac equation for a free electron jt
The Dirac operators a and 6 114
The introduction of an electromagnetic field 120
Electron spin 120
Lorentz invariance of the Dirac equation 125
The negative energy solutions — positrons 128
The non-relativistic approximation of the Dirac equation 131
The method of small components 133
The Foldy-Wouthuysen transformation ts
The free electron 143
Bibliography 153

The Wave Equation for Many Electrons 155

The electromagnetic potentials due to a moving electron 156
The Hamiltonian for two electrons 159
The Breit equation 164
Reduction of the Breit equation to non-relativistic form 166
Radiative corrections 174
The many-electron Hamiltonian 176
Bibliography 178

The Molecular Hamiltonian Lge)

10.1 The introduction of nuclei igo
10.2 Finite nuclear size effects 183
10.3 Spectroscopically useful Hamiltonians 185
10.4 Effective Hamiltonians 188
Bibliography 192
Contents XV

11 The Hydrogen Atom page 194

Let Non-relativistic theory for a one-electron atom 194
Phez The non-relativistic approximation of the Dirac equation U9:
I3 The simultaneous eigenfunctions of j*,j,, /?, s? and K 201
11.4 Commutation relations for the Dirac Hamiltonian 204
175 The Dirac equation in polar coordinates 206
11.6 Solution of the radial equations 207
tty The energy levels 211
11.8 Comparison of Dirac and non-relativistic atomic orbitals 212
LD The Lamb shift 217
11.10 More complicated systems 220
Bibliography 224

IZ Quantum Field Theory 225

|
Fag Quantization of the electromagnetic field 226
122 Solution of the one-dimensional harmonic oscillator equation 230
12.3 Creation and annihilation operators 22
12.4 Photons 234
p25 Zero-point energy and vacuum fluctuations 235
12.6 Fermions and second quantization 237
Bibliography 239

13 The Interaction of Radiation and Matter 241

13:1 The interaction Hamiltonian 242
3.2 Time-dependent perturbation theory 243
13.3 Matrix elements of the interaction Hamiltonian 247
13.4 Absorption and emission 250
£35 Comparison of the semiclassical and quantized theories 254
13.6 Multi-photon processes 256
13 The scattering of photons by molecules 258
13.8 Line widths and resonance fluorescence 260
Bibliography 264

Appendix A Units 265

A.1 SI units 265

A.2 Conversion from the mixed (Gaussian) CGS system to the
SI system 267
A.3 Recommended values of physical constants 268
XV1 Contents

Appendix B_ Vector Relations in Three Dimensions page 270

Appendix C_ General Bibliography 212

Author Index Za

Subject Index 2t7

CHAPTER ONE

Non-relativistic Quantum Mechanics °°"

¥

AS

eel

This introductory chapter has two purposes. The first is to provide a brief
résumé of the quantum theory that is assumed to be familiar to the reader
and, in particular, those results that are used later. A deep discussion of the
foundations of quantum mechanics will not be given and in this chapter the
results will be quoted without proof; the justification for this policy is that
there are a number of excellent texts available. Nevertheless, some of the
mathematics employed in this presentation is discussed in more detail later.
For example, an acquaintance with vector and matrix algebra is assumed here,
although Chapter 2 is devoted to this subject.
The other objective of this chapter is to point out the unsatisfactory fea-
tures of non-relativistic quantum mechanics. This theory is based on a number
of postulates, the justification of which is that the results derived from them
are in agreement with experiment. However, in a relativistic theory some of
these postulates are unnecessary and here we are thinking in particular of elec-
tron spin and the phenomena associated with it.

1.1. Formal quantum mechanics

For convenience just one particle is considered here, but the extension to
many-particle systems is readily made. Moreover, it should be noted that the
present section is not intended to be a logical development of quantum theory.
The state of a one-particle system is described by a wave function W(r, f),
which is a function of particle coordinates and time. The probability of the
particle being found in a small volume dz at position r and time ¢ is given by
W(r, t)*(r, f)dr, where the asterisk indicates complex conjugation. Since the
2 Advanced Molecular Quantum Mechanics

particle must be somewhere in space:

sea, ovr, 0dr = SIVO,d/?d7 = 1 (1.1)

and a wave function satisfying this condition is said to be normalized. Since
the wave function is to be regarded as a probability amplitude, it must be
finite, single-valued and continuous; in addition, it must be possible to per-
form the integration in Equation 1.1. Subscripts may be used to distinguish
wave functions representing different states of a system. Two different wave
functions, V,,, and W,,, are then said to be orthogonal if f ¥7,W,,d7 vanishes.
It is often convenient to use an alternative notation to describe the state of
a system. This is the (bra|c|ket) notation due to Dirac, in which the ket |) is
used instead of W,, and the bra (n| in place of YF. In this scheme Equation 1.1
is written as (n|n) = 1 and the orthogonality condition is (m|n)= 0 (m # n);
in each case integration over all space is implied by the notation. (It is tempt-
ing to say that W,, and |) are equal, but this is not strictly accurate. The W,,
are functions of coordinates, while the |”) are vectors in so-called Hilbert space
and are independent of the coordinate system used. In addition, in the Dirac
notation a quantity such as (n|n) is a scalar product of vectors rather than an
integration over space.)
Observables or measurable properties of a system are represented by oper-
ators. If a state, which is characterized by WY, has a definite value a,, for the
observable represented by the operator A, then W,, is an eigenfunction ofA
with eigenvalue a,, and the equation:

AV, = a,V, (1.2)

is satisfied. By multiplying this equation on the left by W%, integrating over
all space and using Equation 1.1 @,, may be obtained:

Qa, = fUFAW,
dr. (1.3)
This is the expectation value of A in the state m and in the Dirac notation is
written as (n|A|n). In general, expressions of the type f¥mAW,d7 or
(m|A |n) are referred to as matrix elements of the operatorA between states
mand n.
In quantum mechanics the operators are all linear so that the result of
operating on a linear combination of wave functions is:

AlCnVin tenn) = CmAV yjbh ¢, AM. (1.4)

For an operator to represent a physical observable all its eigenvalues must be
real and this imposes the restriction that the operator be Hermitian. The con-
dition for the Hermiticity of A is that the equation:
Non-relativistic Quantum Mechanics 3

SWHAW,dr = f(A*W*)W,,dr = [(W*AW,,)*d7 (1.5)

should always hold or, in the alternative notation, (m|A|n) should always
equal (n|A|m)*. In addition, the eigenfunctions corresponding to different
(real) eigenvalues of an Hermitian operator are orthogonal to one another.
A general normalized function ® can be written as a combination of a com-
plete set of orthogonal functions. This set might be all the eigenfunctions of
the Hermitian operator A:

® = Dc,V,. (1.6)
However, ® is not necessarily itself an eigenfunction of A, but a determination
of the physical property associated with A will always give one of the a,, as
the result; the probability that a particular result a, is obtained being c#,c,.
The expectation value of A in the state represented by ® may still be deter-
mined, but it will be a weighted ayerage of all the eigenvalues a, of A.
A rule is still needed to construct the operator for a particular observable.
It is usual to take the classical expression for the observable and to replace
the position r and linear momentum p by the operators r and p = — ih(0/dr),
respectively, where the symbol / represents ./— 1 and his related to Planck’s
constant A by h = h/2m; the vector operator (0/dr) has components (0/0),
(0/dy) and (0/0z). If both r and p appear in the classical expression then care
must be taken that the resulting operator is Hermitian. In addition, the total
energy E of a system may also be replaced by the operator ih(0/02).

1.2 The Schrodinger equation

Classically the energy of a system is the sum of its kinetic and potential ener-
gies. For a particle of mass m the former is p?/2m and the latter is a function
of position and time:

B= 2m Vest). (1.7)
On quantization the right-hand side of this equation becomes the Hamiltonian
operator:

H = —(h?/2m)(07/dx? + d7/dy? + 97/027) + Vir, 2), (1.8)

where x, y, z are the components of the position vector r. When this operates
on awave function it must give the same result as the energy operator ih(0/0¢),
so that

HW = in(av/ar); (1.9)
4 Advanced Molecular Quantum Mechanics

this is the time-dependent Schrodinger equation.

If the potential energy of the particle is time independent, the Hamiltonian
is also and the space and time variables in Equation 1.9 may be separated. The
solution may then be written:

Wr, t) = exp (—iEt/h) Vr), (1.10)

where £ and w are given by the time-independent Schrodinger equation:

Hy = Ey; a

E is now the energy of the system and is independent of time. In addition,

Equation 1.10 shows that |W(r, t)|?= |W(r)|?, so that these wave functions
describe a stationary state of the system.
Only in very simple cases is it possible to solve the time-independent Schro-
dinger equation 1.11 exactly. In general, approximate methods must be em-
ployed and two approaches are commonly used.
In the first use is made of the variation principle, which states that, if Eo is
the lowest eigenvalue of the particular Hamiltonian, then for any normalized
trial solution w’ of Equation 1.11:

[wHW'dr = Eo. (1.12)

Using this fact a particular form for y’ may be optimized by varying adjust-
able parameters to minimize f ~'*#’dr. In particular, y’ may be taken as a
linear combination of known normalized functions ¢,:

ve = Cnn: (1.13)

and the best approximation of this form to the true lowest eigenvalue of H is
obtained by the variation of the coefficients c,. This leads to a set of coupled
equations:
~ GCA = ES en Gn = 0, (1.14)

where d,,,,, is the matrix element of H between ¢,, and ¢, and S,,, is the
overlap integral f ¢7,¢,d7, which is unity for m =n but is only zero for m#n
if the ¢, are orthogonal to one another.
The other method involves perturbation theory, in which the Hamiltonian
is split into two parts:
I= I dee (1.15)

It is assumed that the eigenfunctions of Ho are known:

HoWn = EnVn (1.16)

Non-relativistic Quantum Mechanics 5

and that the eigenfunctions W,, of the total Hamiltonian may be written as a
linear combination of them. We then have:

and
Wn = Wet D Woinl(Eo—Eo)+...
mtn
(1.17)

Ey = Ent Kan + 2 Hamlmnl(En —Em)+...3 (1.18)

provided H’ is a relatively small perturbation these series converge.

1.3. Heisenberg’s uncertainty principle and related topics

For the wave function describing a state to be a simultaneous eigenfunction of

two operators, A and B, then these operators must commute. That is, AB
must equal BA and this condition is usually expressed as:

[4,B] = AB—BA = 0. (1.19)

If A and B do commute, the observables they represent can in principle be
measured simultaneously and precisely. However, if they do not, there is an
uncertainty in the determined values of the observables and this is expressed
by Heisenberg’s uncertainty principle:

(AA)(AB) > \X[A, B])/2i1; (1.20)

this relates the uncertainties, AA and AB, to the expectation value of the com-
mutator of the operators A and B. In particular, the x components of the
position and momentum operator for a particle do not commute and
(Ax)(Ap,.) 2 h/2. Similarly, the energy operator ih(0/dt) does not commute
with ¢, so that (AE)(At) > h/2 and the precision with which the energy of a
state may be determined depends upon its lifetime.
In this connection we may note that we are using the Schrodinger picture
in which operators such as p and r are time independent and any time depen-
dence of the system is contained in the wave functions, which may evolve
with time. In an alternative formulation of quantum mechanics it is the oper-
ators that are time dependent and the wavefunctions that are independent of
time; this is the Heisenberg picture. It is occasionally useful to know about
the way in which an operator, or one of its expectation values, varies with
time. This section is concluded with a derivation of Heisenberg’s equation of
motion, which can provide this information.
The Heisenberg and Schrodinger pictures of quantum mechanics may be re-
lated to one another by insisting that matrix elements of an operator be the
same in the two pictures:
6 Advanced Molecular Quantum Mechanics

fW*(DA(O)W'(tHdr = S¥*(O)A(HW'(0)dr. (1.21)

Now, an alternative way of writing Equation 1.10 is:

W(t) = exp (— iKt/ny¥ (0) (1.22)

and substitution of this and a similar expression for Y'(¢) into Equation 1.21
shows that:
A(t) = exp (iH t/h)A (0) exp (— ik(t/h). (1.23)

Since A(0) is time independent, the derivative of this equation with respect
to time gives:
dA/dt = (i/h)(HA —AH) = (/h) [H, A], (1.24)

which is Heisenberg’s equation of motion.

As an example of the use of this equation, the velocity operator for a par-
ticle may be determined by setting A equal to r. The appropriate Hamiltonian
is given in Equation 1.8, so that dr/dt = p/m which is what one would expect
by analogy with classical mechanics.
Finally, it may be noted that for any operator A that commutes with the
Hamiltonian its time derivative dA /dt, and the expectation value of this, must
vanish, so that A is a constant of motion. Consequently, the energy and the
observable corresponding to A may be determined precisely and this is in
agreement with the earlier discussion.

1.4 Angular momentum

Classically the angular momentum of a particle is given by r , p, the vector

product of its position and its linear momentum. The corresponding operator
in quantum mechanics is given by the same expression and may be written as:

so that | is a dimensionless operator. The x component is given by:

hl,, = —ih(y 0/dz

— z 0/dy) (1.26)

and the other components may be obtained by a cyclic permutation of x, y

and z.
The components of the operator 1 do not commute:

[eat] a SS He Te eS [ete as ily, (1.27)

so that a wave function cannot be a simultaneous eigenfunction of /,, 1, and /,.

However, the operator = (/, + & + 2) does commute with these components
Non-relativistic Quantum Mechanics Yi

and it is usual to employ wave functions that are eigenfunctions of 7 and ip

Their explicit form may be determined by taking /’ and 1, to be operators in-
volving partial derivatives with respect to spatial coordinates as in Equation
1.26 and solving the resulting partial differential equations. The resulting
eigenfunctions are angular functions, or spherical harmonics, and are charac-
terized by two quantum numbers / and m). The equations they satisfy are:

PY im, = 1+ Wim Wim, = MMV imp (1.28)

where /=0,1,2,...and m,=1,/—1,:..,—-L
Thus an atomic electron is said to possess an orbital angular momentum
which is an integer in units of A. This is in agreement with observations made
in atomic spectroscopy. In addition, experiment shows that associated with
the orbital motion of an electron is a magnetic moment — efil/2m, where — e
and m are the charge and mass of the electron, respectively. (In this book SI
units are employed and these are Summarized in Appendix A; in addition, those
units associated with electromagnetic phenomena are discussed in more detail
in Chapter 5.) This orbital magnetic moment of an electron arises quite natur-
ally in non-relativistic quantum theory when the interaction with electromag-
netic fields is introduced and this is demonstrated in Chapter 7.
Of particular interest is the so-called g factor which is the magnitude of the
ratio of an angular momentum and its associated magnetic moment, the ratio
being measured in units of e/2m. Thus the orbitalg factor is just 1 and this is
not surprising, since classical theory gives the same result. For an electron
moving with speed v in a circle of radiusr the angular momentum is mvr. The
associated magnetic moment is — evr/2, which is just the product of the cur-
rent (— ev/2zr) flowing round the circle and its area (mr’). The ratio of interest
is — e/2m, so that classically the orbital g factor is unity.
Equations 1.28 are obtained by taking the eigenfunctions of I? and 1, to be
functions of the electron’s coordinates. However, a general angular momen-
tum fij may be defined, the components of which satisfy similar commu-
tation relations (Equations 1.27) to Al:

Viesiy) = tes Wyte) = ties Verte] = Hy. (1.29)

Without making any assumptions about the form of the simultaneous eigen-
functions Vim; of the operators j” and j,, these commutation relations may be
used to show that:

PVim; == ae 1 Wim; T2Vimy = MW jm;- (1.30)

These results are analogous to those for P and lL, except that in this case the
values that the quantum numbers may adopt are j= 0, (WieReey OS pear el
8 Advanced Molecular Quantum Mechanics

Ne) lectin aah US half-it. ral angular momentum is possible. For

integer values of/ the eigenfunctions * xy be written as spherical harmonics,
but it is not possible to give the eigenfunction an analytic form when / is a
half integer.

1.5 Electron spin

The existence of orbital angular momentum and its associated magnetic mo-
ment does not explain all the features of the fine structure of atomic spectra
and, in particular, Zeeman splittings. In non-relativistic quantum mechanics it
is necessary to postulate that in addition the electron possesses an intrinsic
angular momentum or ‘spin’ of $ in units of hf together with a spin magnetic
moment of magnitude eh/2m.
The spin angular momentum corresponds to the case j = $ mentioned at
the end of the previous section and by combining spin and orbital angular mo-
mentum the other half-integer values for 7may be obtained. The spin angular
momentum operator is usually deignasted As and the quantum numbers corre-
sponding to j and m; are s(= ) and m,=+ s The eigenfunctions of the
operators s” and s, may then be written as |s, m,) or just |m,), since s is always
5; in addition, the notation |a) and |6) is often used in place of |+ 4) and
|— 5), respectively.
In what follows it is often more convenient to use the operator o = 2s
instead of s itself. The commutation relations for the components of o are
then:
[Gp ssOylen 21025, .[CjmO,| = 210ea, (Osx Onl eee, lod)
and the way in which these operators act on the spin eigenfunctions |a) and
|B) is given by:
0,|a) = |B); 0,18) = |a);
Oyla) = i|B); oy |B) = —ila); (1°32)

o,|a) = |a); o, 18) = —|B).

From these relations the effect of operators constructed from the components
of o may readily be determined. In particular, it may be shown that |) and
|8) are both eigenfunctions of the operators 0%, 03 and o2 with the same eigen-
value 1. Thus we may write:

0, = 0 = o= 1, (1.33)
As we know the commutator of two operators A and B is [A,B] =
(AB — BA). The anticommutator of these operators may also be defined; this
Non-relativistic Quantum Mechanics 9

is just (4B + BA) and is written in the abbreviated form [A, B],. The anti-
commutation properties of the components of o may now be found and as an
illustration we evaluate [0,, oy], by using Equations 1.31:

(Gre Us|, 0,0, + 0,0,

pastes G,1et.o¢locsa,]),
= = sile, o,]. (1.34)
Now, since 0; can be replaced by unity (Equation 1.33), it must commute
with o, and [0,, oy], vanishes. Similarly, the other pairs of components of
may be shown to anticommute so that:

[ox, Oy]+ = [oy, Oz]4 = [02,0x]+ = 0. (1.35)

It should be noted that in general the components of the angular momentum
operator j do not satisfy the relations of Equations 1.33 and 1.35 and that
these properties are peculiar to the case when j = 5.
It is possible to construct a matrix representation of the components ofe,
that is, a set of three matrices which have the same commutation (Equations
1.31) and anticommutation (Equations 1.35) properties and thus mimic the
behaviour of 0,, 0, and o,. This may be done using two-by-two matrices
one such representation being the so-called Pauli spin matrices:

a0 1 0 1 1 0
0». = - Oy = 3 Oz — = (1.36)
j if

These matrices also have the property that the square of each is equal to the
two-by-two unit matrix in agreement with Equation 1.33.
With this formalism the spin functions |a) and |) are written as two-
component column vectors:

1 0
|a) -() Tees |) (1537)
0 1

the complex conjugates of these being the corresponding row vectors. Using
these with Equations 1.36, the relationships of Equations 1.32 may be re-
covered and indeed the elements of the matrices in Equations 1.36 are just the
matrix elements of the corresponding operators between the spin functions.
Electron spin can now be incorporated into the quantum mechanical de-
scription of the electron by using classical analogies to add appropriate spin-
10 Advanced Molecular Quantum Mechanics

dependent terms to the Hamiltonian and using wave functions which are pro-
ducts of spatial and spin functions. The resulting Schrodinger equation can
then be expressed as one equation using the formalism employed in Equations
1.32 or as a pair of coupled equations using the matrix representation of the
spin operators (Equations 1.36) and spin functions (Equations 1.37)
It must be emphasized that although this theory is largely successful it is
based on the postulate of a ‘spinning’ electron with angular momentum fis and
associated magnetic moment — efs/m. The electron spin g factor, which is the
magnitude of the ratio of these two quantities measured in units of e/2m, is
thus 2. This result is contrasted by the orbital g factor of 1 and consequently
the sping factor and the spin magnetic moment are often said to be anomalous.
The reason for this is that, unlike an orbiting electron, it is not possible to con-
struct a satisfactory classical model for a spinning electron.
Any model in which the electron has its mass and charge distributed over a
finite volume explains the existence of both the angular momentum and the
magnetic moment when the electron spins about an axis. However, the g
factor cannot be explained so easily. The simplest model consists of a sphere
with uniform mass and charge densities, but any model in which the mass and
charge are distributed in the same way leads to a spin g factor of 1 just as it
does for the orbital motion of an electron. Of course, if the electron consists
of conducting material the charge might be expected to reside on the surface
of the sphere and this modification of the model leads to a spin g factor of
5/3. Although this is not the required result, it does suggest that models may
be devised with g = 2 and indeed this is so; for illustration we quote just one
such model. In this the electron is a solid cylinder of uniform density and all
the charge resides on the curved surface. The angular momentum is mr?w/2,
where m is the mass, r the radius and w the angular velocity of the cylinder,
and the magnitude of the associated magnetic moment is er?w/2, so that
g = 2 as required.
Nevertheless, this model, and others like it that give a classical g factor of 2,
are rather far-fetched and cannot be taken as a justification for the introduc-
tion of the concept of electron spin. In non-relativistic quantum mechanics
the existence of electron spin angular momentum and its associated magnetic
moment must be regarded as postulates.
All these remarks apply specifically to the electron, but nuclei may be de-
scribed in a similar fashion. They too possess spin angular momenta and mag-
netic moments, although the spin is not restricted to 5 as it is for the electron,
and these properties must also be incorporated in the theory in a phenomeno-
logical manner.
Finally, we might mention a further postulate that is necessary when deal-
Non-relativistic Quantum Mechanics 11

ing with systems of many identical particles. This is the Pauli exclusion
principle, which states that wave functions must be antisymmetric with respect
to the interchange of like particles with half-integer spin and symmetric with
respect to interchange of like particles with zero or integer spin. The former
category of particles, which includes the electron, are called fermions and obey
Fermi-Dirac statistics, while the latter are bosons and are subject to Bose-
Einstein statistics.

1.6 The need for a relativistic theory

The velocity of the electron in the first Bohr orbit of a one-electron atom is
Zac, where Z is the atomic number, a(~ 1/137) is the fine structure constant
and c is the velocity of light. In the hydrogen atom the relativistic corrections
expected are small although they are observable. However, in heavier atoms
these corrections can become quite large for inner electrons despite the shield-
ing of the nuclear charge by other electrons. For this reason alone a relativistic
theory is needed particularly as techniques such as X-ray photoelectron spec-
troscopy are now being used to study the inner electrons in atoms and mole-
cules.
At this point it might be mentioned that we will only be interested in special
relativity. The effects of general relativity, whichis concerned with gravitation,
are negligible in atoms and molecules. This may be seen by considering the
hydrogen atom. In the first Bohr orbit the total energy of the electron is
approximately 2 X 10°'*J, whereas the potential energy due to the gravi-
tational attraction of the electron by the proton is of the order of 2 X 107°7J.
As it happens the incorporation of special relativity in quantum mechanics
gives rise to far greater benefits than might be expected. In particular, it leads
quite naturally to the concept of electron spin, so that this need no longer be
regarded as a postulate. Indeed, both the spin angular momentum and the spin
magnetic moment are predicted by the theory and the spin g factor is found
to be exactly 2. (In fact the spin g factor of the electron differs slightly from
2 and this discrepancy can only be explained by quantum electrodynamics,
which is beyond the scope of this book, although an indication of its origin is
given in Chapter 9).
Morevoer, the spin-dependent terms in the Hamiltonian arise directly from
a relativistic theory and it is not necessary to use dubious classical analogies
to construct them as in the non-relativistic approach. Here we might cite the
spin-orbit interaction, for which classical analogy actually leads to a term
in the Hamiltonian that is twice as large as is needed to explain experimental
observations. It is possible to explain the necessary correction factor classically,
but only if special relativity is included. A section in Chapter 5 is devoted to
V2 Advanced Molecular Quantum Mechanics

this topic, but no problems arise if relativistic quantum mechanics is used from
the outset.
Not only are terms in the Hamiltonian with classical analogues explained
readily in the relativistic theory, but also there are some terms that have no
classical analogues and only appear if special relativity is allowed for.
The theory to be developed in this book applies specifically to particles of
spin 5, and in particular to the electron. However, it turns out that nuclei may
be included adequately in atomic and molecular Hamiltonians by treating them
as electrons but with anomalous masses, charges, spins and magnetic moments.
Finally we note that the Pauli exclusion principle is derivable from relativ-
istic theory, but only by using quantum field theory and as far as electrons are
concerned this is too advanced a topic to be covered in this text, although a
qualitative discussion is given in Chapter 12.
Having made all these assertions about the results that may be obtained by
using relativistic quantum theory, we have now to demonstrate them. However,
before this may be done a certain amount of background theory must be de-
veloped and the next few chapters are devoted to this aim.

Bibliography

Quantum mechanics

Atkins, P. W. (1970), Molecular Quantum Mechanics, Clarendon Press, Oxford.

Dirac, P. A. M. (1958), Quantum Mechanics, Clarendon Press, Oxford.
Eyring, H., Walter, J., and Kimball, G. E. (1944), Quantum Chemistry, Wiley,
New York.
Landau, L.D., and Lifshitz, E. M.(1959), Quantum Mechanics, Pergamon
Press, Oxford.
Murrell, J.N., Kettle,S.F.A., and Tedder, J. M.(1965), Valence Theory,
Wiley, New York.
Pauling, L., and Wilson, E. B., Jr., (1935), Introduction to Quantum Mechan-
ics, McGraw-Hill, New York.
Electron spin
Uhlenbeck, G. E., and Goudsmit, S. A. (1926), ‘Spinning electrons and the
structure of spectra’, Nature, 117, 264: the paper in which electron spin
was postulated.
Kusch, P. (1966), ‘The electron dipole moment — a case history’, Physics
Today, 19 (2), 23: a review of the experiments that showed that the g fac-
tor of the electron differed slightly from 2.
Crane, H. R. (1968), ‘The g factor of the electron’, Scientific American, 218
(1), 72: a description of the experiments now used to measure the electron’s
g factor together with classical models of the electron.
McWeeny, R. (1970), Spins in Chemistry, Academic Press, New York.
Rose*: Chapter 1.

*References consisting of the author’s name only are given in full in the Gen-
eral Bibliography in Appendix C.
 CHAPTER TWO

Vector and Matrix Algebra

It has already been remarked that the reader is assumed to be acquainted with
vectors and matrices, indeed it is unlikely that he will have survived the first
chapter without a rudimentary knowledge of these subjects. However, the
techniques of vector and matrix algebra are used widely in this book and a
summary of these subjects is desirable. This summary could have been rele-
gated to an appendix, but there are a number of sophistications that may well
be unfamiliar, since they do not appear to be covered in elementary mathe-
matical textbooks. The advantages of these sophisticated techniques are that
they provide us with an abbreviated notation and can considerably reduce the
manipulations involved particularly in vector theory.
We start by recalling the elementary theory of three-dimensional vectors.
With this background, the repeated subscript summation convention can be
introduced together with the Kronecker delta, 6;;, and the €;;, notation; it is
the introduction of the latter that leads to the greatest economies. These tech-
niques are used to review the multiplication and differentiation of vectors. The
properties of matrices and determinants are then summarized using the new
notation where appropriate. Finally the possibility of having vectors with four
or more components is mentioned.

2.1. Vectors and vector multiplication

A vector is a quantity that has two properties, magnitude and direction. In

three-dimensional space a vector A may be specified completely by its three
components, Ax, Ay and Az, in three orthogonal directions x, y and z. If unit
vectors in these directions are denoted by e,, e, and e,, then A may be

13
14 Advanced Molecular Quantum Mechanics

expressed as
A = Ae GA ve, tt 4.67, Cay)

Situations arise where it is expedient to change the axis system by rotating

the axes to a new orientation; the vector is unchanged by this rotation, but of
course its components in the new axis system will in general differ from those
in the original axis system.
Two types of vector multiplication will be considered, the scalar product
and the vector product. As their names imply the first results in a scalar quan-
tity, while the second gives a new vector.
The scalar (or dot) product of two vectors A and B is written as A.B and is
defined by:
A.B = A,B, +A,B, +A,B,. QZ)

If A denotes the length of vector A, then the scalar product of A with itself
gives A”:
A.A = A2+A}+A?2 = A?. (2.3)
An equivalent way of expressing a scalar product is:

A.B = AB cos 06, (2.4)

where 6@ is the angle between the two vectors. This angle is clearly unchanged
by a rotation of the axis system, so that the scalar product of two vectors has
the important property of being invariant to rotation. From Equation 2.4 we
note that the scalar product of two perpendicular vectors is zero; two such
vectors are said to be orthogonal. The scalar products of the unit orthogonal
vectors among themselves are thus:

€..C, 1 C76, n—1¢. Ca. =F (2.5a)

CxO ye ue y.0,4 =e nee ,0: (2.5b)

The vector (or cross) product of A and B is written as A , B. It gives a new

vector C, which is orthogonal to both A and B (C.A = C.B = 0) and whose
components are given by:

C, = (A,B), = A,B, —4,B,

Cy = (A,B), =i Be A Be (2.6)
|
ac) = (A,B), = A,By—A,By.
This definition may be expressed more compactly using a determinant:
 Vector and Matrix Algebra 15

e,. ey e,

C= A, B= A. ay | asl (2.7)
By ¥ z

on expansion this gives:

Cea e, (4B, —A,By) i ey (A,B, SAB y) + e,(A,B, —A,By), (2.8)

which is equivalent to Equation 2.6. We note that, unlike the scalar product,
the order in which the vectors appear in a vector product is important, since:

Any one of the four preceding equations shows immediately that the vector
product of a vector with itself vanishes, while in general the magnitude of the
vector A , B is given by AB sin 0, where again 6 is the angle between A and B.
The vector products of the unit orthogonal vectors among themselves are thus:

CrkOe Cys Cyn 2 ez, 0;

Ce REMI AEZ, Vey Rez ©;; (2.10)

ee, = ey.

2.2 The repeated subscript convention for summation

Equation 2.2, which defines the scalar product of two vectors, may be written
in the alternative form:
A.B = 2 A;B;, (On| 1)

where the summation is over i = x, y, z. This equation can be abbreviated still

further:
A.B = A;B;, (2.12)

where the sign indicating summation over 7 has been omitted. The question
arises as to when summation over a subscript is intended and when it is not.
This problem may be solved by introducing the convention that, if a subscript
is repeated, that is, if it occurs twice in an expression, then summation over
all the possible values of the subscript is implied; if a subscript appears only
once in the expression, then we do not sum over its possible values. This is the
repeated subscript convention for summation. It will be seen in the examples
in the remainder ofthis chapter that it is not possible for a subscript to appear
more than twice; if it did the meaning of the expression would be ambiguous
16 Advanced Molecular Quantum Mechanics

and in fact a mistake would have been made. Other checks can be applied to
equations, since a subscript that appears once in one expression must appear
once and only once in all the other expressions in the equation. In addition, a
subscript that appears twice in one expression must appear twice or not at all
in the other terms of the equation. All this should become clearer as examples
are met in the rest of this chapter.
This section will be concluded by using the convention to abbreviate some
of the equations that have been encountered already; in doing this a number
of dangers associated with the convention will be met. For example Equation
2.1 may be written as:
A = Ae; (2.13)
and Equation 2.3 appears as:
A.A = A;A;. (2.14)

The first example presents no problems, but in the second the right-hand side
could have been written as A?, which obscures the fact that the subscript / is
repeated; it is wise to leave it in the expanded form used in Equation 2.14.
Finally, it is tempting to rewrite Equation 2.5a as e;.e; = 1, but this is not cor-
rect, since the subscript i is repeated and summation over the possible values
of imust be performed:

7,6) =) €. Cet €,.0, He), 15. (27-15)

2.3. The Kronecker delta 5;;

We cannot write Equation 2.5a using the general subscript i for x, y and z,
because repeating the subscript i automatically implies summation. However,
Equation 2.5a could be written as:

ee; = 1 fori = J; (2.16a)

Equation 2.5b would then appear as:

ee, = O fori #j. (2.16b)

These two equations could be written as just one equation:

e;.e; = 5;;, (2:17)

if the new symbol, the Kronecker delta, is defined in the following way:

6; = 1 fori =f;
2.18
Vector and Matrix Algebra 17

The Kronecker delta can appear in expressions in a number of different

ways. For example:
6;;4; = Aj, (2.19)
since summation over j is implied. Alternatively, we could encounter the prod-
uct of two Kronecker deltas having a subscript in common:

5ij5nj = Sik; (2.20)

this sort of relationship may be referred to as a sum rule. However, once again
a note of caution should be sounded, since 6;; is not equal to unity, but
instead:
Op-— 0,0 t Oye +65, = 3, (2.21)

since we are now committed to the repeated subscript convention.

Another example of the use of the Kronecker delta is in writing the anti-
commutation relations for the components of the spin vector o, which were
encountered in the first chapter; Equations 1.33 and 1.35 can now be written
with economy as:
[o;, oj], = 25;;. (2.22)

However, the great utility of the Kronecker delta in vector algebra will only
be appreciated when one more symbol has been introduced and this is done in
the next section.

2.4 The €;;, notation

The definition of €;;,, which is known as the permutation symbol or the unit
antisymmetric tensor in three dimensions, is introduced immediately; it will
then be seen how it can be used to simplify equations that have been met al-
ready. If ijk is an even permutation of xyz, then €;;, takes on the value one,
while an odd permutation gives €;;, the value minus one:

Exyz = Evyzx = Czxy = 1

(2.23a)
Exzy = Eyxz = Ezyx = i

There is still the possibility that a pair of the subscripts may be identical, in
which case €;;, has the value zero:

€ijjp = 0 if any pair of i,7, k are identical. (2.23b)

It can now be seen that Equation 2.6 for the vector product of two vectors
may be written as:
C; = (Ay B)i = ijn AjBr- (2.24)
18 Advanced Molecular Quantum Mechanics

This is because the subscripts j and k are both repeated on the right-hand side
of the equation so that, for example:

Cee eA, eee ae

tx yyAyDug Te yyyAyi yh Ceyee yz

+ €xeeA By + €xzyAcBy + CxzeA 2Be

San Pr, Bl2 Jn 2 eee
WA

= A,B,—A,By (225)

by Equations 2.23. Alternatively, Equation 2.7 could be rewritten:

C = (A 4B) = e(€;j;,A;Bp, (2.26)

where summation over i must be performed as well.

The anticommutation of two vectors under the operation of taking a vector
product (Equation 2.9) may easily be demonstrated using this new notation:

A,B = €;€;;,Aj;B, = — €€ 2 ;B,A; = + BicA; (2.27)

since interchange of any pair of subscripts in €;;, must change its sign. In ad-
dition, Equations 2.10, which state the result of taking the vector product of
a pair of unit orthogonal vectors, can now be written as one simple equation:

CAG = Eijrer- (2.28)

So far we have only met products involving two vectors. The triple scalar
product, which is written as A.(B , C), can be expanded using the new notation:

A.(B , C) = €ijpA BC, . (2.29)

From its definition cyclic permutation of the subscripts i,j,k does not alter
the value of €;;,, so that cyclic permutation of the vectors A, B and C does
not alter their triple scalar product:

A(B;.C) =3B(C A) = GC B). (2.30)

The other important type of product involving three vectors is the triple
vector product A, (B,C). This too can be expressed in the new notation:

A A (B A C) = €;€;;,A;(B A C),

= €1€) 24 Jenin? iCm- (2.3.5)

The combination of two permutation symbols in one expression has not been
encountered before. In addition, the subscript k is repeated in the product
Vector and Matrix Algebra 19

Eijk €kim (= €ij€kim), SO that the sum rules involving the permutation symbols
must be considered before Equation 2.31 may be simplified.

2.5 The €;;;, sum rules

The permutation symbol €;;, has been used to express the vector product of
two vectors in terms of their components (Equation 2.26). This was also ac-
complished in Equation 2.7 using a determinant. It would not be surprising if
€;jk Could be expressed as a determinant and indeed it is possible, one way
being:

Eijk = 19jx jy Sz |- (2:32)

Sex Spy Skz

This may easily be checked. From the rules relating to the interchange of rows
in determinants, it can be seen that a cyclic permutation of the subscripts i,j,k.
does not alter the value of the determinant, but a non-cyclic one changes its
sign; thus explicit consideration of, say, €,, shows that this definition is con-
sistent with Equation 2.23a. Agreement with Equation 2.23b may be demon-
strated by noting that if any pair of subscripts are identical, then the determi-
nant will be zero, since two rows are identical. (Any reader unfamiliar with
the manipulations of determinants is reminded that these are summarized in
the section on matrices later in this chapter).
Using the rule for multiplying two determinants together (similar to that
for matrices), the general product of two permutation symbols may be express-
ed as one determinant:

aio:
€ijrElmn — | J*

(2.33)
Sp Onn dkn

this result is best obtained by transposing the second determinant before multi-
plication. Although each subscript appears three times in theabove determinant,
20 Advanced Molecular Quantum Mechanics

expansion leads to a sum of six terms, each of which contains a particular sub-
script once and only once, so there is no inconsistency with the repeated sub-
script convention.
However, if the product €;;,€jmn is under consideration, summation over
i is implied and we have:

EijrEimn — 5 ji 5; 5jn

Sri dem Orn

= 8ji(5jm5rn a 6jnOkm)

rk Sim(Sji5kn an? 6 jnS ri)

+ 8in(5;i5nm — SymSxi)- (2.34)

In evaluating this expression we recall that 5;;= 3 (Equation 2.21) and note
that the Kronecker delta sum rule (Equation 2.20) gives, for example, 5;,,5;;
= 6,,j;- Substitution leads to the first sum rule:

EijrEimn = 5jmOrn —OF,0nm: (23355

Before using this result on the vector triple product, the problem that initi-
ated this discussion of sum rules, two other sum rules will be established. The
first arises when there are two pairs of identical subscripts in the product of
two permutation symbols, for example €;;,€;;,. Equation 2.35 gives immedi-
ately:
€ije€iin = 54j5kn — SjnOrj
38kn — Skn
= 25pn. (2.36)
Finally, for three pairs of identical subscripts:

€ijk ijk = 26 pr = (2.37)

Returning to the problem of the triple vector product in Equation 2.31, use
of Equations 2.35, 2.19 and 2.12 gives:

A (By) ©) = ei€pij€e1mAjBiCn
= €(5;15jm — 5im5j1)AjBiCn
eA ;(B;C; — B;C;)
(A.C)B — (A.B)C. (2.38)
Vector and Matrix Algebra 21

2.6 Examples I

In this section we consider a number of examples of the use of the notation

that has been introduced. The reader is advised to attempt these problems as
exercises before looking at the solutions.

(a) Show that the quadruple vector product (A , B).(C , D) may be expanded
as:
(A , B).(C , D) = (A.C)(B.D) — (A.D)(B.C). (2.39)
Solution:
(A ,B)(C,D) = €;jxAj;Br€imnCmDn

= (6j)m5kn — SjndemJAjBrCmDn
= A;B,CD, — AjB,C,D;

= (A.C\(B.D) — (A.D)(B.C). (2.40)

(b) Express as one equation the commutation relations in Equations 1.31 for
the components of the spin vectore:

[6x 05] 221075 “[0,,.0;]) = 2io,; [6,;.0,] = 2i6,.

Solution:
[0;, 0] = 2i€;;,,0, (2.41)
or multiplying by S€iin€n> expanding the commutator and using Equations
2.26 and 2.36:
ojo = 2ie. (2.42)

(c) Prove the following identity for any two vectors, A and B, that commute
with the spin vector o, but not necessarily with each other:

(o.A)(o.B) = (A.B) +io.(A , B). (2.43)

Solution:

In many of the previous examples, it has been assumed without comment

that all the components of all the vectors commute with one another. In most
of the situations that will be encountered in this book, and in the present ex-
ample in particular, this assumption is not justified and we must keep track of
the order of the vector components. The commutation and anticommutation
relations for the components of ¢ are:
ononmle, (2.42)
22 Advanced Molecular Quantum Mechanics

and
[9;, oj]. = 26;;. (2.22)

To prove Equation 2.43 we note that, since o commutes with A and B, the
term (o.A)(o.B) is identical to the first term on the right-hand side of Equa-
tion 2.39, provided C and D are both set equal too. Equation 2.39 cannot be
used directly, since the order of vector components was not preserved in its
proof, but we can start with the third line of Equation 2.40:

(A A B).(o ao) BS A ;By0; 5, — A;By 0p G;.

Substitution of Equations 2.42 and 2.22 gives:

2io(A A B) = 0;0,A;B, a (= 0; Op ate 26;,)A;Br

20;0;A;B, oad 2A;B;.

On rearrangement and division by 2:

(o.A)(o.B) = (A.B) + io.(A , B);

this is an important relationship and will be used a number of times in Chapter

8 onwards.

2.7 The vector operator V

So far two types of quantity have been encountered, scalars and vectors. Both
scalars and vectors can be functions of time and space coordinates or other
variables. (These two types of functions are usually called scalar fields and
vector fields. An example often given for a scalar field is the temperature,
since this can vary in space and time, but is represented by a scalar quantity
at each point, while an example of a vector field is heat flow, which needs a
vector at each pointin space and time to specify it.) Situations frequently arise
where it is necessary to differentiate a scalar or a vector. Differentiation with
respect to time presents no problems and will not be considered here, but
differentiation with respect to spatial coordinates leads to the vector operator
V.
Let us consider a scalar function $(x, y, z). For infinitesimal increases in
x, y and z the corresponding change in @ is given by:

d@ = (0¢/dx)dx + (0¢/dy)dy + (0¢/dz)dz. (2.44)

This expression can be thought of as the scalar product of two vectors with
components ((0¢/4x), (4¢/dy), (0¢/8z)) and (dx, dy, dz). If the point x, y,z
is specified by the vector r then the second vector may be thought of as dr,
Vector and Matrix Algebra uo

while the first vector consists of the scalar being operated on by a vector
operator with components ((0/0x), (0/dy), (/dz)). This operator is called
‘del’ and has the symbol V:

ll e,.0/dx
V = + e,d/dy + e,0/dz

= e;0/0r; = e; V;, (2.45)

where the repeated subscript convention has again been introduced.

When the operator V operates on a scalar function ¢, there is only one
possible result, a vector V@¢, which is called the gradient of ¢. However, two
possibilities arise when V is allowed to operate on a vector A, since either the
scalar product or the vector product between V and A may be taken. The first
possibility, V.A, is a scalar quantity and is known as the divergence of A, while
the second, V , A, is a vector called the curl of A. The reason for the names,
gradient, divergence and curl, will become clearer when their physical signifi-
cance is considered in the following sections.

2.8 The gradient

The gradient of a scalar function $(x, y, z) is a vector and from Equation 2.45
may be written:
Vo = e,(0¢/dr;) = e;Vi¢. (2.46)
For a small change dr in the position vector r of the point (x,y, z) the corre-
sponding change in ¢ is, from Equation 2.44:

dé = (V¢).dr. (2.47)
To see what V¢ means physically we note that, if k is a constant, the equation
6(x,y,z) = k represents a surface. If dr is taken to be tangential to the surface,
that is the change in position dr takes us to a new point in the same surface,
then dd = 0 and
(V¢).dr = 0. (2.48)

Since dr is tangential to the surface and can be in any arbitrary direction in the
surface, Vd must be perpendicular to the surface. Then again, if dr were not
tangential to the surface, but were to take us to some new surface, d= k’,
Equation 2.47 indicates that the increase in ¢ will be greatest when dr is parallel
to V@, that is perpendicular to the surface. Thus V¢ represents in magnitude
and direction, the maximum rate of increase of the scalar function ¢.
Suppose Equation 2.47 were to be integrated between two points 1 and 2
along some line joining the points. That is for each infinitesimal element dr on
24 Advanced Molecular Quantum Mechanics

the line, we calculate (V¢).dr and then add the contributions from all the ele-
ments of the line. The result would be:

b2—o = J (V9).dr. (2.49)

The left-hand side of this equation depends only on the location of the two
points and is independent of the line along which the integral is performed. It
follows that the line integral on the right-hand side of the equation must also
be independent of the path taken. In the special case where the integration is
over a closed path and point 2 is coincident with point 1:

f, (V¢).dr = $ (V9).dr = 0. (2.50)

2.9 The divergence

The divergence of the vector A has already been defined as the scalar V.A; in
terms of components:

Let us consider the way in which electric charge (or heat etc.) flows out of a
volume element dt= dxdydz centred on the point x,y, z (Fig. 2.1). If the

Face 2 —— Face |

Fig. 2.1. The volume element dxdydz used to demonstrate the significance of
the divergence of a vector.

vector j = j(x, y, Z) represents the current density (flow of charge, or current,

per unit area perpendicular to the direction of j), then the charge loss per unit
time from the volume element through face 1 is:

jx (x + adx, y, 2)dydz ~ [7x + 2(@/x/x)dx]dydz, (2.52)

while for face 2 the rate of gain of charge is:

jg(x — dx,y,z)dydz ~ [j, —3(0j,/x)dx] dydz. (2.53)

Vector and Matrix Algebra 25

The combined charge loss rate through the two faces is thus (0/,./0x)dxdydz.
The charge flow across the other faces of the volume element may be found
in the same way giving for the total charge loss rate from the volume element:

[(0/,./0x) + (0j,/d¥) + (dj,/8z)|dxdydz = (V.j)dr (2.54)

or a loss rate per unit volume of V.j. Thus, sincej is itself a rate, the divergence
of a vector represents a loss per unit volume.
If the charge density associated with the volume element under consider-
ation is p(x, y,z), this loss rate per unit volume could also be expressed as
— (dp/dt) so that the equation:

V.j+(dp/ar) = 0 (2.55)
expresses mathematically the law of conservation of charge, that is charge can
be neither created nor destroyed and any charge lost by a volume element
must go through the surface of thé element.
The rate of loss of charge can also be thought of as an integral over the
surface of the volume element. An infinitesimal surface element may be re-
presented by ds, which is a vector normal to the surface element and with
magnitude equal to the area of the element. Thus the total loss rate from the
volume element is f j.ds, so that from Equation 2.54:

fj.ds = V.j dr. (2.56)

This equation applies to an infinitesimal volume element d7, but it may be
extended to a finite irregularly shaped volume by dividing this volume into
infinitesimal volume elements and integrating. Except at the boundaries of the
volume under consideration any face of a volume element is shared with
another. The loss from one volume element through a shared face is the gain
of the other volume element through the same face and the two cancel on
integration, so that Equation 2.56 generalizes to:

fjds = [V.jdr (2.57)

for an extended region of space; the integral on the left is a surface integral,
while that on the right is a volume integral, the whole equation being known
as Gauss’ theorem.

2.10 The curl

The curl of a vector A, written as V , A, is itself a vector and from Equation

2.26 may be expanded in terms of the components:
26 Advanced Molecular Quantum Mechanics

VA = €;€;jnVjAr- (2.58)

Its physical significance is not as easy to see as in the case of the gradient or
the divergence, but consideration of an area element is instructive. For con-
venience it is assumed to be parallel to the xy plane (Fig. 2.2), but generaliz-
ation to other orientations is possible. The circulation of the vector A round

Fig. 2.2. The surface element dxdy used to demonstrate the significance of the
curl of a vector.

the boundary of the surface element is the line integral round this closed loop
of the component A along the line element, that is $ A.dr. This integral may
be broken down into contributions from the sides of the area element, in the
same way that the contributions from each face of a volume element were
considered when the divergence of a vector was discussed. If the integration
round the boundary of the area element is carried out in the direction of the
arrows in the figure, the contribution from side | is:

A,(x,y— dy, z)dx =~ [A, —3(0A,/dy)dy]dx, (2.59)

while that from side 3 is:

Ax,
y+3dy, z)dx = — [A, + 300A, /dy)dy]dx. (2.60)
The combined contribution from these two sides is — (0A,./dy)dxdy. The
sides 2 and 4 may be treated in the same manner to give for the total line inte-
gral around the boundary of the area element:

¢ A.dr = [(0A,/0x) — (0A,,/dy)]dxdy. (2.61)

The term in square parentheses is just the z component of V , A, while dxdy

is the magnitude of the area element. If as before the area element is repre-
sented by a vector ds normal to it, Equation 2.61 may be generalized to:

gAdr = (V,A).ds. (2.62)

Vector and Matrix Algebra PA|

Thus the circulation of avector round the boundary of an infinitesimal surface

element is the component of the curl of the vector perpendicular to the ele-
ment times the area of the element.
Equation 2.62 may be extended to a general closed loop by taking any sur-
face bounded by the loop and splitting the surface up into infinitesimal surface
elements. Except at the boundary of the surface each edge of a surface element
is shared and the contributions to the line integral from two neighbouring ele-
ments cancel, since the direction of circulation is taken to be anticlockwise in
all elements. Thus:
¢A.dr = f(V , A).ds; (2.63)

the left-hand side is a line integral round a closed loop while the right-hand
side is a surface integral over any surface bounded by the loop. Equation 2.63
is known as Stokes’ theorem.

2.11 Examples II

In this section are given a number of useful relationships involving the vector
differentiation of products; these are also listed in Appendix B for convenience.
If A and B are vectors and @¢ is a scalar, then:

V.(gA) = (V4).A + 9(V.A); (2.64)

Vj, (GA) = (VO), A+ OW AA); (2.65)
V(A.B) = (B.V)A + (A.V)B+ B,(V , A) +A , (V , B); (2.66)
V.(A ,B) = (V,A).B—A.(V , B); (2.67)
V,(A,B) = A(V.B)—(A.V)B + (B.V)A — (V.A)B. (2.68)
In these relationships it has been assumed that ¢ and the components of B all
commute with A so that their order has not been preserved when a simpler ex-
pression results from rearrangement. Consequently care must be used in ap-
plying Equations 2.66 and 2.68 in some situations.
The proofs of these relationships should be regarded as exercises. However,
the proofs of Equations 2.64 and 2.67 will be given here as examples.

(a) Proof of Equation 2.64:

V.(¢A) = V;{(9Ai) = (Vi)A; + O(V;AD)

(V¢).A + ¢(V.A). (2.64)
28 Advanced Molecular Quantum Mechanics

(b) Proof of Equation 2.67:

VA ,B) = Vi(EijxAjBr) = €ijn ((VA)Br + A(ViBx)]

II Epij(ViAj
Br — &irAj(ViBr)
ll (V , A).B— A.(V ;B). (2.67)

2.12 Second derivatives in vector calculus

There are six possible ways in which V can operate twice on a scalar @ or a
vector A: V.(V¢); (V.V)A; V(V.A); V , (Vo); V.(V , A); V A(V , A). There
are no meaningful combinations of the symbols, that are not included in this
list.
The first case, V.(V¢), may also be written without ambiguity as (V.V)¢ or
even V*¢ and the scalar operator V’ expanded in terms of components:
V = V,V; = (02/dx?) + (07/dy”) + (02/827); (2.69)
it occurs frequently in physics and is known as the Laplacian. Since it is a
scalar, the Laplacian can also operate on a vector and an example of this possi-
bility appears second in the original list; however, this possibility is of little
interest as is the third possibility, V(V.A).
The next two cases both vanish as can be seen by rewriting them in alterna-
tive but equivalent ways:

and
V (Vd) = (VAV)o=0 (2.70)
Ve(Vi un Ge = (2.71)
in each case the operator (V , V) vanishes. These two identities have an inter-
esting use. Suppose that the curl of some vector B vanishes, that is (V , B) = 0.
Then Equation 2.70 tells us that, if B is expressed as the gradient of an appro-
priate scalar, the condition that its curl is zero is automatically satisfied. Simi-
larly, from Equation 2.71 it can be seen that, if a divergenceless vector is
written as the curl of another vector, its divergence is guaranteed to be zero.
Finally, we note that the remaining possibility, V , (V , A), may be expand-
ed using Equation 2.68 provided it is remembered that V and A do not com-
mute and their order must be preserved:

V,\(V,A) = VWV.A)— WA. (2.72)

Vector and Matrix Algebra 29

2.13. The Dirac delta function

So far we have been referring to general vectors A, B etc. In the remainder of

this book the position vector r:

ae Pe ia ae ee a Pe IE (2-73)

will often be encountered. In general the result of operating on a component

of r with a component of V is given by:

Virj = (0r;/0r;) = 833. (2.74)

This equation, together with Equation 2.21, immediately tells us that the di-
vergence of r is equal to three:

Va = Viri = 5; = 3. Cas)
On the other hand the curl of r vanishes:

Vat = e€ijnVile = Ci€ijrSjr = Ci€ijg = O- (2.76)

Another simple result that is occasionally useful is:

(A.V)r = A;Vje;r; = eAj5;; = eA; = A, (2.77)

where A is any vector.
A more complicated example, that will be encountered later, is V(1/r),
where r (=(7;7;)?) is the magnitude of the position vector r:
1. . .

Vir) = eV; [ory ?] = e[—r°/2] (Winn)

= —e,[r73/2] [27;6,;] = — er *r;

= — f/r’. (2.78)

We could proceed in the same way to evaluate V°(1/r), which will also be met
later. From Equation 2.78 this is:

Va/r) Vix r/r°) = — V,(r;/r°)

(Vir) — rr)
76, TA ote
Tr)
= 3p ope 0! (2.79)

This suggests that V*(1/r) vanishes everywhere, but is this true when r = 0 and
(1/r) is infinite? Equation 2.78 shows that V(1/r), which is expected to vary
roughly as 7”, also becomes infinite at r = 0 and thus poses no problems. But
30 Advanced Molecular Quantum Mechanics

V(1/r) is expected to behave roughly as 7°, so that it should also be infinite

at r= 0. In fact, Equation 2.79 is incomplete, since it is not true when r van-
ishes, although it is correct for non-zero r.
To demonstrate how Equation 2.79 needs to be modified, the correct result
will first be quoted, since a new symbol needs to be introduced. Equation 2.79
should read:
Vir) = —V.Gir’) = — 40500), (2.80)
where 4(r) is the Dirac delta function (not to be confused with the Kronecker
delta), which is zero everywhere except when r is zero. Now §4(r) is a three-
dimensional delta function and can be factorized into a product of one-dimen-
sional delta functions:

S(t) = S(rx)6(ry)5(7z) = 5()EO)E(), (2.81)

since r is only zero when x, y and z all vanish. We will concentrate for the mo-
ment on the one-dimensional Dirac delta function 5(x), since we can easily
generalize to the three-dimensional case using Equation 2.81.
The function 5(x) is zero everywhere except when x vanishes, but what
happens to 5(x) when x = 0? From what has been said already one might ex-
pect 5(x = 0) to be infinite and indeed it is, but it is defined so that it is infi-
nite in a special way. If f(x) is any function ofx then (x) must satisfy:

Sf )5(x)dx = f(0). (2.82)

In particular if f(x) = 1 then:
f_ d(x)dx = 1, (2.83)

so that 5(x) is zero everywhere except at the origin where it is infinite in such
a way that the area under it is unity.
Thus 5(x) has very strange properties compared with the mathematical
functions usually encountered. However, it can be related to the usual type of
functions in the following way. The function:

(n/m)? exp (— nx’), (2.84)

is plotted in Fig. 2.3 for a number of positive values of n. If this function is
integrated with respect to x between + , then no matter what the value of n
is, the result is unity because there is a standard integral:

[exp (—a?x)dx = Vn/a. (2.85)

From the figure it can be seen that as 7 increases the function (Equation 2.84)
Vector and Matrix Algebra 31

gets spikier at x = 0, and in the limit when n becomes infinite the function
has the same properties as the Dirac delta function 6(x) in that it is zero every-
where except at x = 0, where it is infinite in such a way that the area under it
is unity and Equations 2.82 and 2.83 are satisfied. Thus an alternative defi-
nition of 5(x) is:

d(x) = Et (n/n)? exp (— nx’). (2.86)

Other limits may be used to represent 5(x) and one of these will be encoun-
tered in Chapter 13.

n=\6

ZI
Fig. 2.3. A plot of y= (n/7)2 exp (— nx?) forn = 1, 4 and 16.
\ x

It should be noted that because of its definition the Dirac delta function
can only be used in integrals as in Equation 2.82; however, in this book the
delta function usually arises in quantum mechanical operators, the matrix ele-
ments of which involve integration. Consequently, an operator expression such
as x6(x) may be replaced by zero:

xd(x) = 0, (2.87)
since Equation 2.82 tells us that an integration involving it will vanish. In ad-
dition, Equation 2.82 may be used to show that:

d(cx) = 5(x)/c, (2.88)

where ¢c is a constant.
We Advanced Molecular Quantum Mechanics

It is now possible to demonstrate the validity of Equation 2.80. To do this

some of the results of Chapter 5 are anticipated, but the pertinent ones should
be familiar. It will be recalled that Gauss’ law, which is one of Maxwell’s equa-
tions, may be written in SI units as:

V.E = pleo, (2.89)

where E is the electric field, p the charge density and €o the permittivity in a
vacuum. Now in electrostatics the electric field may be expressed as —V@,
where ¢ is a scalar potential, so that:

V6 = —pleo. (2.90)
In the special case of a point charge q at the origin, the scalar potential at a
point ris given by:
@ = q/4neor. (2.91)

Substitution into Equation 2.90 then gives:

V(/r) = —4np/q. (2.92)

The left-hand side of this equation is the quantity we wish to evaluate; it only
remains to interpret o, the charge density due to a point charge at the origin.
This is zero everywhere except at r=O where it is infinite; in addition the
total charge in space f pdt, must be just q so that:

p = qd(r) (2.93)
is an appropriate description. Substitution into Equation 2.92 gives Equation
2.80, which is the desired result.
In a later chapter the expression V,(7;/r°) will be met. If i#/, reference to
Equation 2.79 shows that it may be expressed as:

Vi(rjlr?) = — 3rz;,[r° i # j), (2.94)

but if i= 7 Equation 2.80 shows that

Vi(rilr*) = 4n8(x), (2.95)

where summation over 7 is of course implied. These two equations may be
written as one:
Vi(7;/r°) oS (477/3)5(r)6;; ote §,;/P° — 3r;ir;[r°, (2.96)

since 6;; = 3 (Equation 2.21) and by symmetry the contributions from each
of the three termsin the summation on the left-hand side of Equation 2.95 are
equal.
Vector and Matrix Algebra 33

2.14 Matrices and determinants: a summary

Although a knowledge of matrices is assumed, it will be useful to summarize

some of the more pertinent properties of matrices using where possible the re-
peated subscript convention, the Kronecker delta and the permutation symbol.
A matrix is merely a rectangular array of numbers. An m X n matrix A has
m rows and n columns, a typical element being 4;; @=1,...m;7=1,...7).
Provided the dimensions are the same, two matrices may be added or subtract-
ed by adding or subtracting corresponding elements; these operations are as-
sociative and commutative. However, the more important operation of matrix
multiplication is in general non-commutative, although it is associative. Again
the sizes of the matrices must be compatible in that an m X n matrix A can
only be multiplied by an n X p matrix B to give an m X p matrix C(= AB) as
the product. The elements of these matrices are related by:

Cir — A; ;Bjr, (2.97)

where summation over j(= 1, . . . 2) is implied by the repeated subscript nota-

tion.
The transpose A of an m X n matrix A is defined as the n X m matrix with
the elements:
Lae (2.98)
It may be shown by a simple application of Equation 2.97 that the transpose
of the product of two matrices is the product of the transposes of the two
matrices but taken in reverse order:

(AB) = BA. (2.99)

There are anumber of specific types of n X 7 or square matrices. A diagonal
matrix is a square matrix in which only the elements on the major diagonal
are non-zero; a special case of a diagonal matrix is the unit matrix I, in which
all the diagonal elements are equal to unity:

The adjoint A* of the matrix A is obtained by transposing the elements and

taking the complex conjugate:

Ate A*. or PAP Ay, (2.101)

A matrix is said to be Hermitian if it is self-adjoint:

At =A. (2.102)
34 Advanced Molecular Quantum Mechanics

A square matrix A has an inverse if there exists a matrix A”! such that:

AAS =A Aue (2.103)

and is said to be orthogonal if this inverse is equal to its transpose:

Aves As (2.104)

on the other hand A is unitary if its inverse is the same as its adjoint:

ASSAY (2.105)

As for the transpose the inverse of the product of two square matrices is the
product of the inverses taken in reverse order:

(AB)! = BUA? (2.106)

as may be checked by substitution into Equation 2.103.
Tr(A) is the notation used for the trace of a square matrix, that is the sum
of its diagonal elements:
Tr(A) = Ajj. (2.107)

It is easy to show that the trace of the product of two matrices 77(AB) is un-
changed by reversing the order of multiplication of the matrices:

Tr(AB) = (AB)ji = AijBji = BjiAij = (BA)jj = Tr(BA). (2.108)

Each n X n matrix A has associated with it a number, the determinant |A |,
which is a sum of products of the elements:

[Al ="d Gal) 4A Ae (2.109)

where the summation is over all permutations of 7,7,...,k and h is the num-
ber of interchanges of pairs of these subscripts necessary to restore the natural
order 1,2,...,. Recalling the definition of €;;, we note that a3 X 3 deter-
minant can be written as:
|A| = €;;,41;A7;A3,, (2.110)
if i,j,k are interpreted as 1, 2,3 rather than x,y,z. The connection between
the determinental definition (Equation 2.7) of the vector product of two
vectors and the definition (Equation 2.26) using €;;, should now be apparent.
From the definition (Equation 2.109) of a determinant a number of useful
properties may be proved: interchange of two rows (or columns) will change
its sign; if two rows (or columns) are identical its value is zero; adding one
row (or column) to another row (or column) does not alter its value etc.
Finally, it may be noted that determinants may be multiplied in the same
way as square matrices and that the determinant of the product of two
 Vector and Matrix Algebra oD

matrices is the product of the determinants of the individual matrices.

A set of 7 simultaneous equations:

A; jx; ay. i,j = ata) (2a)

can be written in matrix form as:

Ax = y, (2412)
where A is an ” X n matrix and both x and y are n X 1 matrices or column
vectors, for example:
ix, \

X2

x= : 5) (2:143)

i |

\Kai

their transposes being | X 1 matrices or row vectors. In fact, a vector in three-

dimensional space can be thought of as a 3 X 1 matrix, and for this reason no
confusion should arise from using heavy type for both vectors and matrices.
The only way in which difficulties might arise is in knowing what size matrix
is intended by a particular symbol. Since the elimination of this problem would
necessitate a clumsy notation, it must always be remembered what size matrix
is denoted by a particular symbol in a particular context.
The formal solution of Equation 2.112 is:

x= Ay, (2.114)
and we recall that the inverse of a matrix is found by finding for each element
A;; its cofactor, which is (— 1)'* times the determinant obtained by removing
row 7 and column /, transposing the resulting matrix and dividing each element
by the determinant of A. That is

(A AvAl (2.115)
where Ajj is the cofactor of element A;,;. If the determinant of the matrix A
vanishes, A is said to be singular and can possess no inverse.
If y = Ax were substituted into Equation 2.112, it would read:

(A—2XI)x = 0, (2.116)
which is the general form of the eigenvalue equation found in quantum mech-
anics; the non-trivial solutions of this set of n equations consists of n values of
36 Advanced Molecular Quantum Mechanics

the eigenvalue ) each with its corresponding eigenvector x. The possible eigen-
values are found by solving the polynomial equation:

iA—AI| = 0 (2.117)
and the eigenvectors x, corresponding to each eigenvalue A, are determined
by back-substitution into Equation 2.116 followed by solution of the result-
ing simultaneous equations. The eigenvectors x, are column vectors, which can
be written side by side as a square matrix X. This matrix X is such that:

X7AX =A, (2.118)

where A is the diagonal matrix with the eigenvalues \,. as the diagonal elements.
Equation 2.118 represents a similarity transformation and in this case it diag-
onalizes the matrix A.

2.15 Vectors in four dimensions

Most of this chapter has been devoted to three-dimensional vectors, each com-
ponent of which corresponds to one of the three spatial dimensions. In the
last section it was seen that these vectors can be thought of as 3 X 1 matrices
and be manipulated accordingly. However, a 3 X 1 matrix is just a special case
of an n X 1 matrix, and such properties as scalar and vector products can be
generalized from three to many dimensions, although it is hard to see the sig-
nificance of say a vector product in n dimensions. But is there any point in
doing this? It is merely noted here that when special relativity is considered in
Chapter 4, it will be convenient to think of time as a fourth dimension, and
that the theory may be developed in terms of four-dimensional vectors or four-
vectors. Further discussion of this topic is postponed till then.

Bibliography

Vectors and Matrices

Arfken, G. (1970), Mathematical Methods for Physicists, Academic Press, New

York: Chapters 1 and 4.
Margenau, H., and Murphy, G. M. (1956), The Mathematics of Physics and
Chemistry, McGraw-Hill, New York: Volume I, Chapters 4 and 10.
Vectors
Feynman, Leighton and Sands: Volume I, Chapters 11 and 20; Volume II,
Chapters 2 and 3.
The Dirac delta function
Arfken, G. (1970), Mathematic
Methods for Physicists,
al Academic Press, Newy
York: pages 69 and 413-417,
 CHAPTER THREE

Classical Mechanics

Before considering special relativity, and in particular relativistic mechanics, a

brief review of classical mechanics will prove useful. This serves two purposes,
to prepare the ground for contrasting special relativity with classical theory
and to review such topics as Lagrangians and Hamiltonians.

3.1 Inertial frames and Galileo’s relativity principle

In this book it is assumed that the motion of electrons and nuclei is indepen-
dent of their dimensions, that is, they may be regarded as point masses or
particles. The justification for this assumption is that electrons and nuclei are
very small compared with the atoms and molecules in which they are found;
the radii of electrons, nuclei and atoms are of the order of 10°7'S, 10°7!4 and
10°'° m, respectively. The position of an electron or a nucleus at a particular
time can thus be specified by its vector position r, that is by three cartesian
coordinates. In general a system of N particles requires 3N coordinates to
specify its instantaneous configuration and the system is said to have 3N de-
grees of freedom.
Although a system can be characterized instantaneously by 3N cartesian
coordinates, other coordinates may be used. Any set of 3N coordinates q,,
(n=1,...,3N), that completely specify the system, is acceptable, and these
are called generalized coordinates; for example, one of these generalized co-
ordinates could be the separation between two particles. However, to be able
to measure coordinates at all, we must have a frame of reference, that is a sys-
tem of coordinate axes and, since the evolution of a system with time is of
interest, a clock fixed in this frame of reference.

57
38 Advanced Molecular Quantum Mechanics

There are an infinite number of possible frames of reference, but the only
ones of interest in classical mechanics are those in which space is homogeneous
and isotropic and time is homogeneous, in agreement with experience. These
frames are called inertial frames and in particular a freely moving particle (one
that experiences no external forces) has a constant velocity in such a frame.
There are still an arbitrarily large number of inertial frames, but these move
uniformly with respect to one another.
Now experiment shows that the laws of physics are the same no matter
what inertial frame is used; this is Galileo’s principle of relativity. Thus, the
same phenomena will be described by similar equations in two different inertial
frames. Suppose that the position of a particle is r in a frame K and r’ in
another frame K’, that is moving uniformly with a velocity v relative to the
first frame K. If the two frames are coincident at time ¢ = 0, then rr andr’ are
related by the Galilean transformation:

r=r+vt. (3.1)
It will be noted that time is here assumed to be the same in the two frames,
t=t'. It is this assumption that time is absolute that distinguishes a classical
theory from a relativistic one; special relativity will be considered in the next
chapter, and for the remainder of this chapter it will be assumed that time is
indeed independent of the inertial frame used. With this assumption an equa-
tion expressing a physical law must be invariant to the transformation (Equa-
tion 3.1); that is, the equation must have the same form in different inertial
frames.

3.2 The principle of least action

The state of a mechanical system is completely specified at an instant of time,

if all the generalized coordinates q,, are known. If all the generalized velocities
Qn (= dqn/dt)are also known at the same instant of time, then in principle the
subsequent motion may be calculated. This is achieved by setting up equations
of motion relating the coordinates g,,, the velocities g,, and the accelerations
Gn- Solution of these equations for the q, as functions of time, enables the
evolution of the system to be followed.
One way of obtaining the equations of motion would be to use Newton’s
laws. However, there are other formulations of classical mechanics and the one
given here, the principle of least action or Hamilton’s principle, is the most
important. This principle may be shown to be consistent with Newton’s laws,
but neither should be regarded as a consequence of the other; they are alterna-
tive fundamental postulates.
Classical Mechanics 39

The principle of least action states that a system may be characterized by

the Lagrangian £L(qn, Gn, t), which is a function of the generalized coordinates,
the generalized velocities and also the time. The motion of the system between
two times, fg and fy, at which the coordinates are known, is such that the
action S, which is defined by:

takes the least possible value. Thus, the action is a line integral along the path
taken by the system between f, and f, and the path actually followed is such
that the action is least. (Strictly speaking this is only true for an infinitesimally
short path and the condition for a finite path is that the action should have a
stationary value; however, it will be seen that in deriving the equations of mo-
tion from the principle this point is of no consequence.)
It is not easy to visualize the physical meaning of the least action principle.
However, there are other minimum principles in physics, the most transparent
being Fermat’s principle of least time, which states that light travels between
two points in such a way that the time taken is a minimum. Use of this princi-
ple leads immediately to the rectilinear propagation of light in a uniform
medium, the laws of reflection at a surface and the laws of refraction for light
crossing the boundary between two different media. For detailed discussions
of this principle the reader is referred to the bibliography at the end of the
chapter.

3.3 Lagrange’s equations of motion

By minimizing the action (Equation 3.2) equations of motion may be obtain-

ed. For simplicity this will be done initially for a system characterized by only
one coordinate qg, the extension to many degrees of freedom being made later.
The fixed values of g at times f, and f, are taken to be qq and q, (see Fig. 3.1).
Let us suppose that the function of time q(t) represents the path along which
the action integral is minimized (or in general has a stationary value). A slight
displacement from this optimum path to a new path, q(t) + 5q(2), can have no
first-order effect on the action, that is the corresponding change 4S in the ac-
tion integral is zero:
6S = 6 S,>L(q,4q,t)dt = 0. (3.3)

This may be expanded as follows:

40 Advanced Molecular Quantum Mechanics

q,Odt
5S = fio 6Lq,

= sto [(aL/q)5q + (8L/aq)oq]dt = 0. (3.4)

It might be thought that, since the Lagrangian is a function of time, a term

involving (0.£/0f) should appear. However, in varying the path we are interested
in the change in the Lagrangian for each line segment of the action integral,
that is each change is considered at a fixed time. Since 5q dt is the’ same as
d(5q), the second term in Equation 3.4 may be integrated by parts:

ae fe RM d (aL
SS (®) 7: a (e)-2(] 6q dt-= 0. (3.5)

Now the first term in this equation vanishes, since g is required to have the
fixed values gq and qy at times t, and f,, so that 5g(t,) and 5q(tp) are both

{Sl Fae ee
ee aS ES ee

git) +8q (1)

Biswsn |e The path taken by a one-coordinate system between (qq, t,) and
(4p, ty); q(t) is the path along which the action is assumed to be least and q(t)
+ 6q(t) is a slightly displaced path.

zero. Thus, the integral in Equation 3.5 must vanish and this must be true for
any arbitrary infinitesimal change in path 5q. The only way that this can hap-
pen is for the integrand to vanish also:

d(ac\ af _ 4
dt\aqg) aq or
 Classical Mechanics 41

This result may be generalized to a system with many degrees of freedom.

Corresponding to each generalized coordinate q,, there can be an arbitrary in-
finitesimal change in the line integral, so that there will be an equation similar
to Equation 3.6 for each coordinate:

H
dt \ag,
a OE
E gts
FYE bes
ps
(ead 2s, SV): (3.7)

These equations are known as Lagrange’s equations of motion (or Euler’s equa-
tions in the general context of the calculus of variations, which is the mathe-
matical technique that has been used here). These partial differential equations
may be solved for the particular system under consideration to give the g,, ex-
plicitly as functions of time; in general, there will be 6N arbitrary constants,
which may be fixed by initial conditions.
Of course, the form of the Lagrangian must be known before the equations
of motion may be solved. Before considering this in the next section, it is
noted that the equations of motion are unaltered by multiplication of the
Lagrangian by an arbitrary constant; however, the same constant must be used
for all Lagrangians, if isolated systems are to be brought together and treated
as one with a combined Lagrangian. In addition, a Lagrangian is undetermined
to the extent that addition of a total time derivative of a function f(@n,t)of
coordinates and time will not affect the equations of motion. This may be
seen by noting that addition of (df/dt) to the Lagrangian adds to the action
integral (Equation 3.2) a term:

Si (df/dt)dt = [f(qn,t)]{ = constant, (3.8)

since the g,, are assumed fixed at t, and f,. Consequently such a term can have
no influence in the variation procedure used in developing the equations of
motion.

3.4 The Lagrangian for a system of particles

It has already been stated that the principle of least action is consistent with
Newton’s laws and indeed they may be derived from the principle via Lagrange’s
equations of motion. The derivation given here is not completely rigorous, but
the consistency of the two approaches should be apparent. It is first necessary
to obtain an appropriate Lagrangian and this is done for a free particle before
_considering a collection of particles.
The Lagrangian of a free particle in an inertial frame cannot depend on the
vector position r of the particle, since this would imply that space was not
42 Advanced Molecular Quantum Mechanics

homogeneous, nor can it depend on the time explicitly, if the homogeneity of

time is to be preserved. This means that the Lagrangian can only involve the
velocity r of the particle. However, the isotropy of space demands that it must
be independent of the direction of the velocity so that it must be concluded
that the Lagrangian of a free particle can only be a function of r’, that is
L£(r?). Substitution of this result into Lagrange’s equations of motion (Equa-
tion 3.7) gives immediately:

L OL
d Ds =) Ole asa Ss CONStANt. (3.9)
dt \ar or

(When the derivative of a scalar with respect to a vector is written, we mean

the vector whose components are the derivatives of the scalar with respect to
the corresponding component of the vector. Thus the second of Equations
3.9 represents three equations, a typical one being (0£/07,)= constant).
Since the Lagrangian is a non-linear function of the velocity, the velocity
itself must be constant. This gives the first of Newton’s laws, that in an
inertial frame a free particle moves with constant velocity.
The precise form of the Lagrangian may be determined by appealing to the
law of relativity, since on performing a Galilean transformation (Equation 3.1)
between two inertial frames the equations of motion must be unchanged so
that the Lagrangian can only be changed by at most the addition of a total
time derivative of a function of coordinates and time. This can be shown to be
possible only if the Lagrangian is directly proportional to 7”; to agree with
other approaches to classical mechanics the proportionality constant is taken
to be $m, where m is the mass of the particle:

(Se (3.10)
The Lagrangian in the K’ inertial frame of Section 3.1, which is related to the
present frame by the transformation of Equation 3.1, is then given by:

L = amy = ym(t —v)’

= tmr— mtv + km?

= £L—d(mr.v— imvt)/dt. (3.11)

This separation of £’ into £ and a total time derivative would not be possible
if the Lagrangian were a more complicated function of 7? than Equation 3.10.
For a system of particles the Lagrangian is the sum of the Lagrangians for
the individual particles together with a term representing the interaction be-
tween the particles and this can only be a function of the positions of the par-
Classical Mechanics 43

ticles. If the particles are distinguished by the subscript i, the total Lagrangian
may be written:
t= Z ymir} — Vir;) = T(t)— Vir). (3.12)
The first term is the kinetic energy T while V is the potential energy; the reason
for these names and the presence of the minus sign will become apparent in
the next section. The repeated subscript summation convention is not appro-
priate for the first term, since the subscript i differentiates particles and not
vector components. Substitution of Equation 3.12 into Lagrange’s equations
of motion (Equation 3.7) gives three equations for each particle:

By interpreting — (0V/dr;) as the vector F;, the force on particle i, Newton’s

second law is obtained, the Equations 3.13 being Newton’s equations of mo-
tion which equate forces with mass accelerations.
Up till now the discussion has been in terms of cartesian coordinates, but a
transformation may be made to any appropriate generalized coordinates. The
kinetic energy is in general a quadratic function of generalized velocities, but
cross terms can appear and the coefficients may be functions of the coordi-
nates. However, the Lagrangian may still be written in terms of the kinetic
energy T and the potential energy V:

£= Tn; aes = V(qn)- (3.14)

Since the kinetic energy can also be a function of the generalized coordinates,
the generalized force F,, must be defined as:

F, = (£/@qn). (3.15)
Earlier it was stated that the Lagrangian can also be a function of time, and
this occurs if the particles are subject to some sort of time-dependent external
potential; this possibility will be encountered later.

3.5 Constants of motion

For a closed system, that is one that is not subject to an external potential,
there are a number of functions of the coordinates and velocities that remain
constant throughout the motion. Of these constants of motion the most im-
portant are those that are a direct consequence of the homogeneity and isotropy
of time and space. Here they will be derived using cartesian coordinates, al-
though the extension to generalized coordinates will be discussed.
44 Advanced Molecular Quantum Mechanics

The homogeneity of time implies that for a closed system the Lagrangian
does not depend explicitly on time. Thus:

(d£/dt) = D [(OL/dr;).r; + (OL/dr;).4;]. (3.16)

Substitution for (0L£/0r;) using Lagrange’s equations of motion (Equation 3.7)

gives:
d£ ed POL OO se

we 7 ede) * Ga)
S Ciba VOL\ 4a da . |of

se at alae)
i en
Rearrangement of this equation shows that:

E = 24,(a£/at;) —L, (3.18)

does not vary with time and is a constant of motion. Substitution of the ex-
plicit Lagrangian (Equation 3.12) for a system of particles now gives:

E = T(;) + Vigj). (3.19)

E is the total energy of the system, and is composed of two parts, the kinetic
energy J, which is a function of the velocities, and the potential energy V,
which is a function of the coordinates only. When generalized coordinates are
being used, the equations analogous to Equations 3.18 and 3.19 are:

EB = ¥ qn(0Lll0gn)
—£ = Tan, dn) +Vdn)- (3.20)
Since space is homogeneous an arbitrary infinitesimal displacement & of a
system of particles must leave the Lagrangian unaltered:

6£ = 2 (dL£/dr;).8 = 6.2 (dL£/dr;) = 0. (3.21)

Since 8 is arbitrary, this can only be interpreted as showing that:

2 (o£/dr;) = 0, (3.22)

or using Lagrange’s equation of motion (Equation 3.7):

d(ae\ dw(ae
S (2) ' Plea =O) (3.23)
U
Classical Mechanics 45

Thus ~ (0£/dr;) is a constant of motion and is called the total momentum of

the system. It is clear that, unlike the energy, momentum is additive and each
particle has associated with it a momentum:

pi = (dL£/dr;); (3.24)
substitution of the Lagrangian (Equation 3.12) shows that this is equal to m;t;.
In addition, substitution of Equation 3.24 into Lagrange’s equations of motion
and use of Equation 3.13 shows that:

D; 3 (0L£/dr;) = — (dV /or;) = F,, (3:25)

where F; is the force on particle 7. From this equation it is apparent that Equa-
tion 3.22 shows that & F; = 0 and in particular for a system ofjust two par-
l

ticles we may recover Newton’s third law, that to every action there is an equal
and opposite reaction.
Equations 3.24 and 3.25 may be generalized:

By OL/0g,)) Fy = (CL oda )= Fi, (3.26)

where p,, is a generalized momentum and is said to be conjugate to the coordi-
nate g,. The energy (Equation 3.20) can now be written in the simpler form:

UE Ft (3.27)
Finally, the isotropy of space implies that the Lagrangian is invariant to in-
finitesimal rotations of the axis system. Use of this condition leads to a third
constant of motion, the angular momentum. The rotation of a system of par-
ticles through an angle 66 may be represented by a vector 66 directed along
the axis of rotation, the sense of the rotation being given by the right-hand
screw rule. If the axis passes through the origin of the coordinates, the ro-
tation changes a position vector r by an amount 6r= 66, r and the change
in the time derivative of r is given by 5r = 60 , r. The corresponding change
in the Lagrangian is thus:
bL£ II >» [(0L/dr;).6r; + (0.£/0r;).54;]

lI > [p;.68 , 1; + p;-58 yr]

50. [d(=l 1; , pi)/d¢], (3.28)

where Equations 3.7 and 3.24 have been used for (d£/dr;) and (0£/dr;). Since
£ isinvariant to rotation, 5£ must vanish and, because 5 is arbitrary, Equation
3.28 shows that:
L= 24, Pi (3.29)
46 Advanced Molecular Quantum Mechanics

is a constant of motion. This is the angular momentum and as for the linear
momentum it is an additive property of a system of particles.

3.6 The Hamiltonian

The Lagrangian is a function of coordinates and velocities, but it is often more

appropriate to describe a mechanical system in terms of coordinates and mo-
menta; for example, quantum mechanics is usually formulated in terms of
momenta rather than velocities, although in that case the momenta are, of
course, operators. The equations of motion may be rewritten in terms of mo-
menta in the following way. The total differential of the Lagrangian expressed
in terms of generalized coordinates is:

d£ = ¥(0L/8qn)ddn + ¥ (BL/24n)
Gn. (3.30)
where again a closed system is assumed so that the Lagrangian does not depend
explicitly on time. Substitution of Equations 3.26 into Equation 3.30 gives:

df = = (Pnddn + Pndgn)

Il x [Pnddn e d(GnPn) —Gn4Pn] ’ (3.31)

or on rearrangement:

dH = d( GnPn — £) = x [adds a Gn Pn] : (3.32)

The new symbol # represents the Hamiltonian:

Hn, Pn) = = dnPn =o, (3.33)

and reference to Equation 3.27 shows that it is just the energy of the system.
Hamilton’s equations of motion may now be obtained directly from Equation
3:32

If the Lagrangian of a system is known as a function of coordinates and

velocities, the corresponding Hamiltonian may be found as a function of co-
ordinates, velocities and momenta from Equation 3.33. However, the Hamil-
tonian is a function of coordinates and momenta alone and the dependence on
velocities must be removed for it to be useful. This may be done by using the
first of Equations 3.26 to obtain the momenta as functions of the velocities
and coordinates, solving this set of 3V simultaneous equations for the velocities
as a function of coordinates and momenta and substituting in Equation 3.33.
Classical Mechanics 47

As developed here, the Hamiltonian is a function of coordinates and mo-

menta, but like the Lagrangian it may also depend explicitly on time if the
system is not closed. However, it will be seen in Chapter 5 that external poten-
tials may be included without modification of the above equations.

Bibliography

Classical mechanics

Goldstein, H. (1950), Classical Mechanics, McGraw-Hill, New York.

Landau, L. D.,and Lifshitz, E. M. (1960), Mechanics, Pergamon Press, Oxford.

The principle of least action and Fermat’s principle

Atkins, P. W. (1970), Molecular Quantum Mechanics, Clarendon Press, Oxford:
pages 27-31.
Feynman, Leighton and Sands: Volume I, Chapter 26; Volume II, Chapter 19.
CHAPTER FOUR

Special Relativity

The theory of classical mechanics, which was discussed briefly in the previous
chapter, is classical in two senses. First, it is not a quantum mechanical theory
and is thus not appropriate on a molecular scale. Secondly, it takes no account
of special relativity. The use of the word ‘classical’ is thus ambiguous, since in
different contexts it may mean non-quantal or non-relativistic or both. It is the
purpose of this chapter to remove one of the restrictions and develop a rela-
tivistic but non-quantum-mechanical theory for a free particle.

4.1 Einstein’s principle of relativity

The relativity principle, that the laws of physics are the same in all inertial
frames, has been met already in Section 3.1. However, the Galilean transform-
ation (Equation 3.1) used there to relate inertial frames, is based on the as-
sumption that time is absolute, that is the time interval between two events
will be the same no matter what inertial frame is being used. We will see that
this assumption is not in fact correct.
Experiment shows that, if two particles interact in some way, a change in
one does not have an instantaneous effect on the other, but that there is a
finite time lapse between the cause and the effect. This in itself points out a
difficulty with classical (non-relativistic) mechanics, since the interaction is de-
scribed by a potential energy that is taken to be a function of the particle
positions alone, an assumption that implies the instantaneous propagation of
interactions. If there is a finite delay between cause and effect, there must be
a maximum velocity of propagation of interaction that determines the mini-
mum delay before a change in one part of a system begins to affect another

48
Special Relativity 49

part. The existence of a maximum velocity of propagation means that a par-

ticle cannot move faster than this velocity. In addition, the principle of rela-
tivity tells us that this maximum velocity of propagation must be the same in
all inertial frames and is thus a universal constant. In fact it is the velocity of
light in a vacuum, c = 2.997925 X 10° m s"'. By linking the principle of rela-
tivity with a finite maximum velocity of propagation of interaction, Einstein’s
special principle of relativity is obtained and the theory based on it is said to
be relativistic in contrast to the non-relativistic theory based on an infinite
velocity of propagation.
The non-relativistic theory of Chapter 3,and in particular the Galilean trans-
formation (Equation 3.1), may now be seen to be inconsistent with Einstein’s
theory ofrelativity. Differentiation of Equation 3.1 with respect to time shows
that in non-relativistic theory velocity vectors may be summed and in particu-
lar the velocity of light will be different in different inertial frames in contra-
diction to the principle of relativity. These assertions are in agreement with
the experiments of Michelson and Morley, who showed that the velocity of
light does not depend on its direction of propagation, despite the fact that the
earth is moving. Of course, the fact that non-relativistic mechanics is wrong
does not invalidate Newton’s laws and the mechanics associated with them.
Because the velocity of light is so large, deviations from a non-relativistic theory
are usually negligible and the classical theory is a very good approximation in
most cases. The relativistic equations that are derived in this chapter may be
used to calculate the discrepancies between the two theories and, if we pretend
that the velocity of light is infinite, that is if we revert to a non-relativistic
theory, these discrepancies vanish.
If the Galilean transformation (Equation 3.1) is not correct, time cannot be
absolute and must evolve differently in different inertial frames. The time
lapse between two events will depend on the inertial frame used and this must
be specified. In addition, two events occuring in different parts of space may
be simultaneous when observed from one inertial frame, but they will not be
simultaneous in other frames. The fact that it must now be thought of as being
relative, puts time on the same footing as spatial coordinates and it is often
convenient to think of a four-dimensional space in which an event is described
by three space coordinates and one time coordinate. Points in this space are
called world points to distinguish them from points in three-dimensional space
and the history of a particle is described by a world line. For a particle that is
moving with a constant velocity in a straight line the corresponding world line
is straight.
50 Advanced Molecular Quantum Mechanics

4.2 The interval

Although time is not absolute and the time lapse between two events depends
on the inertial frame used, there is another quantity, the interval, that is inde-
pendent of the inertial frame.
To demonstrate this the invariance of the velocity of light is first expressed
mathematically. Suppose that in an inertial frame K a signal leaves the point
X1, ¥1,2Z1 at time ¢, with velocity c and arrives at another point x2, V2, Z2 at
time ty. The distance between the two points may be related to the time taken
by the signal to travel between them:

[on — x)? + O2—?+(a—zyP—eh-t) = 0. 9 (4.0)

In another frame K’ the same signal travels between the world points x},
yi,
Z1, t and X9, V9, Z2, f, and a similar equation may be written:

[0g — x)? + OLD? + (a 2)" -—eA — 4) = 0. (4.2)

This suggests that for any two events with world points x1, ¥1, 21, ; and X2, y2,
Z2,t2in K the quantity:

iy = [c7(t2 = 0k =a Coen xi —Or2 Vi) = (as z)°F? (4.3)

is of importance; S12 is called the interval between the two events. Since the
velocity of light is the same in all inertial frames, Equations 4.1 and 4.2 show
that, if the interval s;. between two events in K is zero, the interval sin K’ for
the same two events also vanishes.
If the two events occur at two world points that are infinitesimally close to
one another and whose coordinates are separated by dx, dy, dz, dt in K, then
the interval ds is given by:

ds” =) 7dt? dx? dy? dz (4.4)

the corresponding interval ds’ in K’ is given by a similar equation and as before
if ds= 0 then so does ds’. In addition, the principle of relativity requires that
the laws of physics are the same in the two frames so that the transformation
from dx’, dy’, dz’, dt’ to dx, dy, dz, dt must be linear and homogeneous (no
additive constants). Consequently, ds’” must be a homogeneous quadratic func-
tion of dx, dy, dz, dt just as ds is. It can now be seen that, since ds’ vanishes
whenever ds does, no matter what the values dx, dy, dz and dt take, ds’? can
differ from ds* by at most a multiplicative factor k:

ds'’* = kds?. (4.5)

The coefficient k cannot depend on space or time coordinates, since this would
Special Relativity S

imply that different points in space and time are not equivalent, in contradic-
tion to the homogeneity of space and time. Thus it can only depend on the
relative velocity v of the two inertial frames K and K’. However, the isotropy
of space demands that k cannot depend on the direction of the relative motion
of the two frames and & can only be a function of the magnitude of v. If ds”
had been expressed in terms of ds’* the corresponding equation to Equation
4.5 would have been:
ds? = k'ds’?, (4.6)
where k’ is the same function of the magnitude of — vas kis of the magnitude
of + v. Consequently k = k' and comparison of Equations 4.5 and 4.6 shows
that k must be + 1. The negative solution can be dismissed immediately, since
ds’? must tend to ds? as the relative velocities of the two frames tends to zero,
so that:
dss ds (4.7)
Similarly ds’ must tend to ds as v tends to zero and ds = ds’. Integration to
give finite intervals then gives the final result that the interval between two
events is invariant to the inertial frame used:

Si = Sp, (4.8)
and this invariance may be attributed to the fact that the velocity of light is
the same in all inertial frames.

4.3 The Lorentz transformation

Now that the interval between two events has been shown to be invariant to
the inertial frame used, the explicit transformation between space and time
coordinates in different frames can be found. Two inertial frames K and K’ are
again considered and for simplicity it is assumed that the x and x’ axes coin-
cide, and the y and z axes are parallel to the y’ and z’ axes, respectively; the
velocity of the frame K’ relative to K is v along the x axis (see Fig. 4.1).
It has already been noted that time is not absolute and that it is convenient
to think of a four-dimensional space in which one of the coordinates is related
to time. The time and space coordinates may be made equivalent by introduc-
ing the new time coordinate:
T = ict, (4.9)

since the interval (Equation 4.3) between two events is then given by:

Sin = —[(t.— 11) + 2 — 1)? + 2 — v0)? + (22 — 21)’), (4.10)

52 Advanced Molecular Quantum Mechanics

so that, if 7 is the coordinate associated with the fourth dimension, the inter-
val is related to the distance between two points in four-dimensional space.
The transformation from one inertial frame K with coordinates x, y,z,7 to
another K’ with coordinates x’, y’,z’, 7’ can thus be thought of as a transform-
ation in four-dimensional space. Since the interval is independent of the inertial
frame, the length of a line must be preserved in such a transformation, that is
only orthogonal transformations are of interest.

Fig. 4.1. The relationship between the inertial frames K and K’.

All orthogonal transformations may be broken down into rotations and

parallel displacements of the coordinate system. The latter are of no interest
since they only change the origins of the space and time coordinates and a
‘mixing’ of space and time is required. Any rotation can be resolved into six
rotations parallel to the six orthogonal planes xy, yz, zx, xT, yT, ZT in the four-
dimensional space. The first three of these account for the usual space rotations
and of the last three, which mix space and time, a rotation parallel to the x7
plane is chosen for specific consideration, since the y and z coordinates will
not change, as in the model that has been chosen for consideration (Fig. 4.1).
For an orthogonal rotation through an angle 0 in the x7 plane:

x = x’ cos@—7' sin;
} (4.11)
T =x’ sinO +7 cos@.
To relate @ to the relative velocity v ofK and K’, the motion of the origin of
the K’ frame is considered, that is x’ is set equal to zero. Substitution in Equa-
tions 4.11 gives:
x = —T sind; T= T cosO, (4.12)
or combining these:
tan @ <=. ==)7: (4.13)
Special Relativity 53

Now, if the origins of the two frames are assumed to coincide at T= t = 0, the
origin of the K’ frame has the coordinate x = vt = — ivt/c in the K frame,
where Equation 4.9 has been used to relate ¢ and r. Substitution in Equation
4.13 now gives:
tan0 = iv/c. (4.14)

Using familiar trigonometric relations, sin @ and cos 8 may now be recovered:

sin@ = tan @(1 + tan? 6) = ivy/c;

: (4.15)
cos@ = (1+ tan?6)? = y,
where y is defined as:
¥ = —v{c%V2. (4.16)
The transformation (Equations 4.11) now become:

% = ¥(x' —iv7'/c);
(4.17)
tT II= y(ivx'/o+7').

Finally the time coordinate ¢ may be reintroduced using Equation 4.9 to give:

x = ¥@' £vr); pe ays

(4.18)
sect L= yx
Je +7).
as the Lorentz transformation for the model under discussion, in which K’
moves with velocity v along the x axis relative to K.
The transformation (Equations 4.18) may be inverted:
,
x yx— vt); yay;
(4.19)
AE? ip t = y(— vx/c? + 0),
where the definition (Equation 4.16) of y is unaltered. This inversion is most
easily performed by noting that, if the primed and unprimed coordinates are
interchanged in Equations 4.18, the roles of the two frames are also reversed
and v must be replaced by the velocity ofK relative to K’, that is by — v.
One of the checks that can be applied to relativistic equations is that, if the
velocity of light c is permitted to become infinite, the correct non-relativistic
equations should be recovered. In this case Equations 4.18 become:

ee Piuraye ee ee Sr, (4.20)

which are appropriate Galilean transformation equations for the situation under
consideration (cf. Equation 3.1).
54 Advanced Molecular Quantum Mechanics

Of course, the Lorentz transformation of Equations 4.18 applies to the

special case when the space axes of the two frames are parallel and their rela-
tive motion is along the x axis. Any problem may be reduced to this situation
by an appropriate transformation of the space coordinates in the two frames.
However, in the more general case where the spatial axes of the two frames
are parallel, but the relative motion is characterized by a general vector v, the
transformation may be written as:
r= r tyv[(ve'\(y— 1)? + 70’);
(4.21)
t= y{vr)/c* + 2];
the proof is left as an exercise.
Finally, we note that all relativistic equations expressing physical laws must
be invariant to the Lorentz transformation, just as all non-relativistic equations
must be invariant to the Galilean transformation (Equation 3.1); this is the
principle of relativity. Indeed, the reason that Lorentz’s name rather than
Einstein’s is linked with the transformation is that Lorentz had found earlier
that Maxwell’s equations of electromagnetism are invariant to this transform-
ation rather than the Galilean transformation. It is for this reason that it is
appropriate that electromagnetic theory is developed relativistically as in
the next chapter. Invariance to transformations is generally expressed in the
theory of groups and Lorentz transformations can be shown to constitute
a group, though this fact is not pursued here.

4.4 Contraction, dilation and paradoxes

In this section some of the more entertaining of the consequences of relativity

are briefly discussed, although a result which will be used later is obtained in
the process.
The length of a rod, which is at rest in the inertial frame K and lies parallel
to the x axis, is Ax = x2 — x , where x2 and x, are the coordinates of the ends
of the rod. In the frame K’, which is moving along the x axis with velocity v
relative to K, the length of the rod, Ax’ = x3 — x‘, will be different. This length
may be calculated by using the first of Equations 4.18 to determine x’; and x>
at time ¢’ in terms of x, and x2:

xy = Vite); x2 = ye2+v1'). (4.22)

Elimination of ¢' and use of Equation 4.16 gives:
Ax’ = Ax/y = Ax(1 —v2/c?)2, (4.23)
If the first of Equations 4.19 had been used instead, the positions x4 and
x2 would have been determined at two different times ¢', and f}, as can be seen
Special Relativity 55

from the last of Equations 4.19. In the method used here the times at which
xX, and x2 are determined is not important, since the rod is at rest in K. From
Equation 4.23 it can now be seen that the length of the rod in K’, the frame
in which it is moving, is less than the length in its rest frame K. This shortening
is known as the Lorertz (or Fitzgerald) contraction.
A similar phenomenon occurs when time lapses are considered. For a clock
that is at rest in the K frame and is consequently moving at velocity —v in the
K' frame, the time between two events that occur at eee ater wander ets
At = t, — t. The corresponding time interval, Ar’ = t3 — f',, in K' may be ob-
tained from Equations 4.19:

pss Y(t, + vx/c?); es Y(t2 + vx/c?) (4.24)

from which:
At’ = yAt = At(1 —v?J/c?y?. (4.25)
Here the fact that x has the same value for each event has been used; if Equa-
tions 4.18 were used, allowance would have to be made for the fact that the
value of x’ is different for the two events. Equation 4.25 shows that the time
(Ar) measured by a moving clock is always less than the time (Ar’) measured
in the rest frame. This phenomenon is known as time dilation.
The infinitesimal interval ds is given by Equation 4.4. Now a clock measures
the time in its own rest frame so that the infinitesimals dx, dy and dz are all
zero and cdt = ds. Thus the time lapse measured by a clock is:

AVAL a Syaaa ett ilies FPS (4.26)

where the second integral is a line integral along the world line of the clock. If
the clock is at rest, its world line will be straight and parallel to the ¢ axis and,
as we have seen, it will indicate a greater time than if it had been subjected toa
journey which returned to its starting point. Thus the line integral f ds isa
maximum for a straight world line joining the world points a and b. Although
this fact has been established for a world line parallel to the ¢ axis, that is for a
clockat rest, the integral will be a maximum for any straight world line, since the
interval s is independent of the inertial frame used and a straight world line in
one frame will be straight in all other inertial frames. This result may be inter-
preted as showing that the length of a line between two world points is great-
est when the line is straight! However, this is not as ridiculous as it seems, since
one of the coordinates, 7 = ict, in the four-dimensional space is really imagin-
ary. The fact that fR ds is a maximum for a straight world line will be used in
the next section.
56 Advanced Molecular Quantum Mechanics

Both the Lorentz contraction and time dilation are real phenomena, though
after more than half a century the paradoxes associated with them are still
discussed frequently and there are those who remain unconvinced. We will
confine our discussion to one experimental manifestation of time dilation and
one of the paradoxes associated with it.
Mu-mesons, which are created by cosmic rays in the upper atmosphere at a
height of approximately 10* m, are observed on the ground. Their observed
lifetime in the laboratory is only 2 X 10°°s suggesting that those reaching the
ground must travel at velocities of the order of 10c! However, the lifetime
measured in the laboratory is appropriate for the rest frame of a mu-meson
and, as a result of time dilation, the lifetime will be greater by a factor of
(1 — v?/c?)? in a frame in which the mu-meson is moving with velocity v. Mu-
mesons with velocities close to that of light can thus reach the ground before
they decay.
One of the more famous paradoxes is the so-called clock paradox. If two
clocks are synchronized in the rest frame and one then undergoes a round-trip
at high velocity, on its return the travelled clock will be found to be running
slow relative to the other as a result of time dilation. The paradox arises when
it is argued that the two clocks should run at the same rate, since there is a
symmetry between them in that their roles could be reversed by choosing a
different rest frame. However, although this symmetry between the clocks
exists when they are moving uniformly with respect to one another, it is not
present during the acceleration and deceleration that the travelling clock must
experience during its journey.

4.5 The transformation of velocities

Ina relativistic theory velocities cannot be added vectorially, since it would be

possible to have a resultant velocity greater than that of light. To see how
velocities should be combined, the way in which velocities transform from one
inertial frame to another must be considered.
The two inertial frames K and K’, that are illustrated in Fig. 4.1, are used
again. The Lorentz transformation, Equations 4.18, may be written in terms of
infinitesimals:
dx y(dx' + vdt’); dy = dy;
(4.27)
dze=ides dt = y(vdx'/c? + dt’).
Division of the first of these equations by the fourth gives the x component of
a velocity u in the K frame in terms of the corresponding component of u’ the
velocity in the K’ frame:
Special Relativity 57
ele ee th vt i tell Hie
oS arde vdx'/e?+ dt’ 1 tulv/e?’ Cee)
similarly:
uy = uy/y +uv/c?); uz = u,/yQ +u)v/c?). (4.29)
Unlike the y and z components of a position vector the corresponding com-
ponents of a velocity are changed in this transformation, since time intervals
are changed. Equations 4.28 and 4.29 both give the classical equations, if c is
made infinite.
For a particle moving with velocity wu’ parallel to the x’ axis in the frame
K', Equations 4.28 and 4.29 show that in the K frame it moves parallel to the
x axis with a velocity u given by:

u= (u +v)/(1 +u'v/e’). (4.30)

This equation expresses the result of adding two velocities, and can be seen to
reduce to the classical result, w = u’ + v, for low velocities. In addition, it is a
simple exercise to show from Equation 4.30 that the relativistic sum of two
velocities can never exceed the velocity of light.

4.6 The relativistic mechanics of a free particle

In the classical (non-relativistic) mechanics of the last chapter, Newton’s second

law implies that a particle can be accelerated to any velocity by the continued
application of a force. This is relativistically impossible, and there must be an
increased resistance to acceleration as the particle’s velocity approaches the
velocity of light; indeed, this resistance must become infinite in the limit that
the particle has velocity c. The reason that the classical theory is unsatisfactory
is that the equations of motion are not invariant to a Lorentz transformation,
which is necessary for relativistic validity. Of course, this does not mean that
Newton’s laws are wrong; they work very well when low velocities are involved
and the corresponding relativistic equations approximate to them for such
situations. However, the theory of Chapter 3 needs modification when high
velocities are considered. In fact, the only change necessary is in the Lagrangian
used, since invariance to a Galilean transformation was only invoked to deter-
mine the explicit form of the non-relativistic Lagrangian of a, free particle
(Section 3.4).
The principle of least action (Section 3.2) requires that the action integral S
has a minimum for actual motion between two situations, a and 5, specified
by coordinates and times. Thus S can be thought of as an integral along a world
line between two world points. Now S must be independent of the inertial
58 Advanced Molecular Quantum Mechanics

frame used and must therefore be a scalar, since Lorentz transformations do

not preserve the magnitudes or directions of vectors. This means that the inte-
grand of the action integral must be a scalar as well as being a first-order differ-
ential. The only scalar that satisfies these conditions is the infinitesimal interval
ds, which is defined in Equation 4.4. Thus:

Sa Ld
b ds, (4.31)

where k is a constant and a and bare two world points. The sign of k is nega-
tive, since the action is required to be a minimum for actual motion and it was
seen in Section 4.4 that fe ds is maximum for a straight world line and could
be made arbitrarily small by a suitable choice of a curved world line.
From Equation 4.4 ds is given by:

ds = (c?dt? — dx? — dy? — dz’?

= cdt(1 — u2/c?)?, (4.32)
where u is the velocity of the particle. Substitution in Equation 4.31 gives:

S = k stoc( — ufc dt,

a
(4.33)
which may be compared with the definition (Equation 3.2) of the action inte-
gral in terms of the Lagrangian:
SSap Pode
a
(4.34)
showing that relativistically:

£ = kel —wcry. (4.35)

The constant k characterizes the particle and may be determined by compar-
ing this Lagrangian in the classical limit with the non-relativistic Lagrangian of
Chapter 3, which in the current notation is just smu’. Expansion of Equation
4.35 as a power Series in (u/c) gives:

£ = ke—jke(ulcy+...; (4.36)
the first term may be ignored, since it is a constant and makes a contribution
to the action integral (Equation 4.34) that is independent of the path of the
integral. If k is taken to be — mc the second term reduces to }mu? and the
remaining terms all vanish in the classical limit. The relativistic Lagrangian for
a free particle is thus:
£= —me1 — Jc). (4.37)
Special Relativity oY

From this Lagrangian the momentum and Hamiltonian of the particle may
be determined from the definitions of the previous chapter. Using Equation
3.24 the momentum of the particle is:

= (8£/du) = mu(1 — u2/c?y?, (4.38)

The Hamiltonian is given by Equation 3.33 to be:

H = pu-—L = me —wv2I/c?)?. (4.39)

Of course, to be useful the Hamiltonian must be expressed in terms of the mo-
mentum rather than the velocity, but Equation 4.38 may be used to eliminate
u from Equation 4.39. This is achieved most easily by noting that:
2
*cA°(1 — w/c?) = mc + [me7u2/(1 — u?/c?)]
= m*c* + c*p*. (4.40)
The required result is thus:
KH = e(m’c? + p?)?, (4.41)
where the positive square root has been taken to agree with the non-relativistic
limit.
When c isallowed to become infinite, the momentum (Equation 4.38) goes
over to the classical expression mu as expected, but the Hamiltonian (Equa-
tion 4.39) becomes infinite! This difficulty may be avoided by expanding H
as a power series in (u/c) and then neglecting terms in (u/c)* and higher. This
gives:
H = me? + 5mu?, (4.42)
similarly, in the non-relativistic limit Equation 4.41 reduces to:

HK = mc? + p?/2m. (4.43)

Both of these expressions are the same as the non-relativistic ones except for
the presence of an extra term mc’. This term is present even when the particle
is at rest and is called the rest energy.
In this book the mass m of a particle is taken to be a constant independent
of velocity, but an yoety! such as 4.39 may be viewed in a different way by
rewriting it as =Mc’, where M, which is still thought of as the mass, varies
with velocity and is related to the rest mass m by M= m(1 — u/c? y? . Thus,
when a particle is accelerated the energy it gains may be associated with its extra
mass, suggesting that all mass is a manifestation of energy, even the rest mass.
These ideas led to the famous equation F = Mc’ and are supported by experi-
ments involving nuclei and fundamental particles in which mass and energy are
interconverted.
60 Advanced Molecular Quantum Mechanics

4.7 Four-vectors

It has already been noted that time may be thought of as a fourth dimension
and that the location and time of an event may be represented by a world
point in four-dimensional space. The position of this world point may be speci-
fied by a vector with four components ry (a= 1, 2,3, 4), where ry, r2 and
r3 are the spatial coordinates x, y and z respectively and rg is related to the
time coordinate. To distinguish this type of vector from those in three-dimen-
sional space, they are called four-vectors and here Greek subscripts are used to
label their components.
By analogy with three-dimensional vectors the scalar product of the position
four-vector with itself is defined as:

holo = Titiht+i+ ri, (4.44)

where the repeated subscript convention is again used, but since a four-vector
is involved, the summation is over the four possible values of the subscript a.
If r4 is to chosen to be 7 = ict (Equation 4.9), then Equation 4.44 becomes:

Fat Oe ae ay (4.45)

and the scalar product 74/7, is invariant to Lorentz transformations, since it is

then directly proportional to the square of the interval s (see Section 4.2).
With this choice of rq the Lorentz transformation (Equations 4.18) is:

Fy C1
— Weal). rr rr:
(4.46)
rg = Y(ivrilc + 74),
where y retains its original meaning (Equation 4.16).
A general four-vector may now be defined as one having components that
transform in precisely the same way as the rg under a Lorentz transformation.
With this definition the scalar product of any two four-vectors, for example
A, By, is invariant to such transformations and is independent of the inertial
frame used, as can be seen by expansion of the product.
Although it was not at all obvious, there were four quantities in the pre-
vious section that constitute the components of a four-vector. The way in
which the components of the momentum p (Equation 4.38) of a particle be-
have under a Lorentz transformation may be established using Equations 4.28
and 4.29, which describe the transformation of velocities. The algebra is simple
but tedious, and will not be given here, the result being that the components
of p are the spatial components, p;, p2 and p3, of a four-vector the correspond-
ing time component being p4= i#(/c, where H is the particle’s Hamiltonian or
Special Relativity 61

energy (Equation 4.39). It follows from the invariance of the scalar product
of two four-vectors that pyPq should be invariant:

DuDot Dade (4.47)

from Equation 4.41 this is just equal to — m’c?, where m is the rest mass of
the particle, confirming that it is indeed invariant.
The Lorentz transformation can be thought of as an orthogonal transform-
ation in four-dimensional space. This means that, in addition to scalar products
being invariant, any expression or equation that can be written entirely in
terms of four-vectors will be unchanged by a Lorentz transformation. Of course
the components of the four-vector will be changed, but in the new frame the
expression or equation will have the same form as in the old and the physical
content will be unaltered. This behaviour is analagous to the three-dimensional
situation, where the meaning of a vector equation is independent of the ortho-
gonal axis system used. Thus, by writing an equation in a four-vector notation
its Lorentz invariance is automatically ensured.
The Lorentz transformation of the position four-vector can be written gen-
erally as:
Toe = Gaple- (4.48)
The agg are the components ofa four-by-four matrix, and, since the trans-
formation is orthogonal, this matrix is orthogonal and the components satisfy
the relations (cf. Equation 2.104):

the inverse relation to Equation 4.48 is thus:

rp = ope (4.50)
Now under the transformation the operator (0/0r,,) transforms as:

(0/8rq) = (8rg/Arq)(8/9r8)
= dog (0/0rg), (4.51)

so that (0/dr.) is the component of a four-vector operator. Other four-vectors

will be encountered in the next chapter.
The concept of four-vectors, the components of which transform in the
same way as the rg, can be extended to four-tensors, the components of a four-
tensor of rank n transforming in the same way as products of n components of
the position four-vector. Thus a four-tensor of rank one is just a four-vector,
while a four-tensor of rank two has sixteen components Fyg (a, 68 = 1, 2, 3, 4)
62 Advanced Molecular Quantum Mechanics

which transform in the same way as the sixteen quadratic products ryrg, that
is:
Fag = Lay4Bé Frys a (4.52)

Four-tensors of higher rank are defined in an analogous fashion and examples

of four-tensors will be encountered in the next chapter. The advantage of
using a four-tensor notation is that any equation that can be written entirely
in terms of four-tensors will automatically be Lorentz invariant.
The theory of four-vectors may be developed further along the same lines
as for three-vectors; for example the permutation symbol €ggy¢5 can be intro-
duced. However, any further discussion will be postponed till it is needed.
Finally, it should be noted that many texts use superscripts as well as subscripts
to distinguish the covariant and contravariant components of vectors. This dis-
tinction is not necessary in the special theory of relativity; indeed, we would
gain nothing from this sophistication and the price would be greater com-
plexity.

Bibliography

Special Relativity
Feynman, Leighton and Sands: Volume I, Chapters 15—17.
Goldstein, H. (1950), Classical Mechanics, McGraw-Hill, New York: Chapter 6.
Landau and Lifschitz: Chapters 1 and 2.
Rindler, W. (1966), Special Relativity, Oliver and Boyd, Edinburgh.
CHAPTER FIVE

The Interaction of Charged Particles

with Electromagnetic Fields

So far we have been concerned with the mechanics of a free particle, and the
possibility of a particle interacting with an electromagnetic field must now be
considered. This willlead naturally to a discussion of the electromagnetic field
itself. It has already been noted that Maxwell’s equations, which describe elec-
tromagnetic fields, were found to be invariant to Lorentz transformations
rather than Galilean transformations and that this discovery preceded Einstein’s
theory of special relativity. Consequently it is appropriate that electromagnetic
theory should be developed from a relativistic stand point, although this was
not the case historically. The approach used here is a logical one, but of course
the final justification of the theory is that it agrees with experiment.

5.1 Units

It is at this point that a decision must be made about units. In mechanics the
transition between different systems of units is trivial and usually involves
only factors of 10. However, in electromagnetic theory the appearance or non-
appearance of the factors 47, c, €9 and Uo depends on the system of units
adopted.
In the past the system of units used by chemists and chemical physicists
has usually been the mixed or Gaussian system, which is based on centimetre-
gramme-second (CGS) units, but in which magnetic quantities are measured in
electromagnetic units (e.m.u.) and electrostatic quantities in electrostatic
units (e.s.u.). Because of the way these units are defined, equations connecting
the two sorts of quantity contain factors of c. This appearance of c is not a
consequence of special relativity, but merely reflects the separate initial
63
64 Advanced Molecular Quantum Mechanics

development of electrostatics and magnetostatics; in a relativistic theory these

scaling factors involving c are confusing. In addition, since there is no separate
dimension for electromagnetic properties in the CGS system, the dimensions
of electromagnetic quantities involve square roots. Finally, in equations using
the mixed system of units factors of 47 appear when they are not expected
geometrically, and do not appear when they are.
It has now been agreed internationally that the Systéme International (SI)
should be used for units. Although the transition from the old system to the
SI system is not trivial, it will be adopted here, since it has definite advantages.
First, the ampere is employed as a fundamental unit in addition to the metre,
kilogramme and second, that is the units are based on an MKSA system. This
means that square roots no longer appear in dimension expressions. Secondly,
all electromagnetic quantities are expressed in units coherent with these four,
so that the scaling factors involving c no longer appear; when c does appear in
an equation it is usually a consequence of special relativity. Thirdly, the sys-
tem is rationalized in that factors of 47 only appear where they are expected
on geometrical grounds.
There are other consequences of the adoption of SI units. In the mixed sys-
tem the permeability and permittivity of free space, Uo and €o, are dimension-
less constants and are frequently omitted from equations, since they are both
equal to unity. However, in the SI system they have dimensions, are not equal
to unity and must be included in equations. In addition, the magnetic field
strength H is often used instead of the magnetic flux density Bin the mixed
system, since they are equal in free space, although observable physical proper-
ties depend on B. In the SI system B and H differ by a factor of Ug = 4 X 10°”
kgm s 7A” and equations must be written in terms of B.
The details of the SI system as far as electromagnetic phenomena are con-
cerned will appear at appropriate points in the text. These details are summar-
ized in Appendix A together with a few comments on the conversion from the
mixed CGS system to the SI system.

5.2 The electromagnetic potentials

The relativistic mechanics of a particle was developed in the last chapter by

using the principle of least action. The appropriate action integral was seen to
be (Section 4.6):
S = J? (— me ds), (5.1)

where s is the interval and the integration is performed between the world
points @ and b. If the particle interacts with an electromagnetic field, further
The Interaction of Charged Particles with Fields 65

terms have to be added to this action integral, and these terms will involve
quantities characteristic of the particle and the field. The extra terms must, of
course, be Lorentz invariant, but beyond that little can be said about them
and an appeal to experiment is necessary. That is, the justification of the terms
that will be added is that the equations that they lead to are in agreement with
experimental observations.
Experiments indicate that only one new parameter, the charge q, is needed
to characterize a particle as far as its interaction with an electromagnetic field
is concerned, but that four quantitiesA, (a= 1, 2, 3, 4), which are functions
of time and the position of the particle, are needed for the field. The Ay are
the components ofa four-vector and thus under a Lorentz transformation they
behave ina similar manner to the rg, the components of the position four-vec-
tor. The spatial components, A;, A2 and A3, are the components of a three-
dimensional vector A, which is called the (magnetic) vector potential, while
the time component A q is related to the electric or scalar potential ¢ by:

Aa = idle. (5.2)
A theory that agrees with experiment may be developed by taking the inter-
action terms in the action integral to be:

i oqgAcin. (5.3)
the integrand is proportional to the invariant formed by the scalar product of
the potential four-vector and the infinitesimal position four-vector, which has
components dry.
The total action integral thus appears as:

S = S°(—meds + qA.dr — godt), (5.4)

where the scalar product in Equation 5.3 has been expanded in terms of scalars
and three-dimensional vectors. The corresponding Lagrangian may be extracted
from the action by recalling that (Equation 4.32):

ds = c(1 —w2/c?)2dt, (5.5)

where u is the velocity of the particle:

u = dr/dt. (5.6)

Substitution for dr and ds in Equation 5.4 gives:

S = sie [mel —w[c?¥ + gA.u—adlde, (5.7)

66 Advanced Molecular Quantum Mechanics

and comparison with the definition (Equation 4.34) of the action integral in
terms of the Lagrangian £ shows that:

£= —me7(1— u/c?) + gA.u— q¢. (5.8)

The introduction of an electromagnetic field can thus be accounted for by the

addition of two terms to the Lagrangian.
The momentum of the particle is given by Equation 3.24:

p = 0£/du = mu(l — {023 +qA

=nm+qA, (5.9)

where tris called the mechanical momentum, that is the momentum in the ab-
sence of the field; p is the total momentum conjugate to the velocity u and is
distinguished from w by being referred to as the canonical momentum. The
momentum of a particle is thus modified by the addition of aterm involving
the vector potential A.
Equation 3.33 gives the Hamiltonian of the particle:

H = pu—L = mcX(1—uJc?2)?
+ go. (5.10)
This may be expressed more appropriately in terms of the canonical momen-
tum p in the same way that Equation 4.41 was obtained for the case of no
field:
H c[mc? + (p—qA)’]? + a
= ¢(m2c? + 1)? + go. (5.11)

Comparison of Equations 5.9 and 5.11 with Equations 4.38 and 4.41 shows
that to generalize from a free particle to a particle in a field, all that is necessary
is to replace p by wm= (p—qA) and KH by (H —q@). For example, the non-
relativistic limit of the Hamiltonian (Equation 5.11) is, by comparison with
the non-relativistic field-free Hamiltonian (Equation 4.43):

HK = mce?+qotn7/2m. (5.12)
In the SI system of units the charge g has dimensions TA, while the vector
and scalar potentials, A and ¢, have dimensions MLT 747! and ML?T 34“1, res-
pectively. For the mixed system of units Equations 5.9 to 5.12 are only modi-
fied in that the mechanical momentum must be rewritten as:

m= p—(qicA, (5.13)
where the factor c_! has no relativistic significance; however, there are other
hidden differences, since the dimensions of g are modified to M!2L3?7T~! and
A and ¢ have the same dimensions M21 }27~!.
The Interaction of Charged Particles with Fields 67

5.3. The field vectors

Now that the Lagrangian for a charged particle in an electromagnetic field is

known, the particle’s equations of motion may be determined from the Lag-
range equations 3.7, which for a single particle may be written as:

a (al) _ = by:
dr\du ory Pet Gi

It is first noted that (0L£/du) is by definition the canonical momentum p =

(w+ qA), while the operator (0/dr) is just the operator V, so that Equation
5.14 can be rewritten as:

(dn/dt) + q(dA/dt)— VEL = 0. (5.15)

Now, since A is a function of space and time coordinates:

(dA/dt) = (0A/dt) + (dr;/dt)(dA/dr;)

= (dA/dt) + (u.V)A. (5.16)

In addition, the gradient of the Lagrangian (Equation 5.8) is:

VEL = qV(A.u) — qV¢

= q[(u.V)A +u ,(V ,A)] — V9, (5.17)

where use has been made of the vector relation, Equation 2.66, and the fact
that u does not depend explicitly on r. Substitution of Equations 5.16 and
5.17 into Equation 5.15 followed by rearrangement gives finally:

(dnfdt) = qu,(V , A) +q[—Vo—(@A/02)). (5.18)

The term (dr/d?¢) is just the force on the particle, since in the classical limit
this reduces to m(du/df).
The right-hand side of Equation 5.18 has been separated into a velocity de-
pendent part and a velocity independent part, so that this equation may be
rewritten as:
(dn/dt) = qu,» B+ gE; (5.19)

in this form it is known as Lorentz’s equation. The vector B is called the mag-
netic flux density and is defined by:

B= V,A, (5.20)

while the electric field strength E is given by:

E = — V¢-—(0A/9t). G21)
68 Advanced Molecular Quantum Mechanics

In a vacuum B and E together completely specify the electromagnetic field,

but in media other than free space two additional vectors are needed, the mag-
netic field strength H and the electric displacement D. In the mixed system of
units B and E are respectively the same as H and D for the special case of a
vacuum and in particular H is frequently used (incorrectly) in place of B. How-
ever, this equality does not occur when the SI system is used and it is necessary
to distinguish B and H. From now on we will only be concerned with B and E,
and when we refer (loosely) to a magnetic or electric field, it is to be under-
stood that these are characterized by the magnetic flux density B and the elec-
tric field strength E.
From Equations 5.20 and 5.21 B and E may be seen to have the dimensions
MT™~*A™' and MLT °A"', respectively, in the SI system. In the mixed unit sys-
tem Equation 5.20 is unaltered, but the term involving A in Equation 5.21 is
modified by a factor of c”'; again the dimensions in the mixed unit system are
more complicated than this implies.

5.4 The Lorentz transformation of electric and magnetic fields

The components of the magnetic flux density B and the electric field strength
E are related to the components of the four-potential A, and the position
four-vector rg by Equations 5.20 and 5.21. We might enquire how these com-
ponents behave under a Lorentz transformation. It will be seen that they trans-
form in the same way as quadratic products of the components of two four-
vectors, that is as the components of a four-tensor of second rank.
The sixteen quantities Fg (a, B = 1, 2, 3, 4), which are defined as:

Fag = (0Ag/dr_) — (0AQ/Org), (5.22)

are components of a second rank four-tensor. Since the A, are components of

the four-potential, they behave in the same way as the components of the
position four-vector (Equation 4.48) under a Lorentz transformation, that is:

Ag = agAg. (5.23)
In addition the operators (0/07) were shown to be the components of a four-
vector (Equation 4.51):
(0/dra) = ag(0/0rg), (5.24)
so that:
Fog = AquyAg6 Fs; (5:25)

comparison with Equation 4.52 shows that the Fg are indeed the components
of a four-tensor. However, explicit consideration of these components (Equa-
The Interaction of Charged Particles with Fields 69

tion 5.22), and use of Equations 5.20 and 5.21 shows that they are related to
the components of B and E; this relationship may be indicated by a matrix-
like array:

0 £. =B 5 HEC
a 0 Be ei) ea
(fan) = : : (5.26)
B, —B, 0 —iE,|c
EESopens! RS Cola ak
PiesFa 0

Thus the components of Band E are related to the components of a four-tensor,

which is called the electromagnetic field tensor and which is antisymmetric,
since Figg = — Fey.
The transformation properties of the Fyg and hence the components of B
and E may now be determined. As usual the special case depicted in Fig. 4.1 is
considered, that is the a = 2 and/3 components of a four-vector are unaltered
by the transformation. Thus F32, 33 and F433 are unchanged, while Fy and
Fz transform as the a= 1 anda =4 components of the same four-vector; the
same remark applies to Fj3 and F'43. The remaining components are related to
these because of their antisymmetry, except for F},, Fj4 and F'44, which can
easily be shown to be unchanged for an antisymmetric four-tensor. We con-
clude that Fug = Fag except for:

Fy = YF 2— ivF 4/c); Fa = YivF pp/c + Fa); (5.27)

es 1(Fi3— ivF43/c); Fag = Y(ivF i3/c + Fag).

By identifying the Fyg with the components of B and E (Equation 5.26), we

obtain:
By = Ba By= yB,—vE lc); B, = CPve,
tIc); (5.28)
yo, Be — (eet 8) B= (VB,
Finally, these equations may be generalized to the case where the primed frame
moves with a general velocity v relative to the unprimed frame; for the non-
relativistic limit v <c, they take the particularly simple form:

Be teh ice E=E—vy,B. (5.29)

The magnetic flux density and the electric field strength are thus interrelated,
so that if one vanishes in one frame of reference it will not necessarily be zero
in another. For example, a particle that is moving in an inertial frame in which
there is a magnetic field, but no electric field, will nevertheless experience an
electric field in its own rest frame.
70 Advanced Quantum Molecular Mechanics

For a four-vector, with components Fy say, one can construct a quantity

that is invariant to Lorentz transformations; this quantity is just the scalar
product FF. One would expect to be able to construct invariants from the
components Fag of the electromagnetic field tensor. Since the Fag transform
as products of pairs of components of four-vectors, one such invariant will be
Fyghyg, Where summation over both a and @ is implied. Expanding this in
terms of B and E gives:

Fogag = 2(B?— E?/c”) = invariant; (5.30)

this may be checked by explicit use of Equations 5.28.
There is another invariant of second degree this being E.B. However, it is
not a true scalar in that it changes sign on inversion of the coordinate system,
that is when r is replaced by —r. This may be seen by noting that ordinary
vectors suchas A and V also change sign and are called polar vectors; Equation
5.21 shows that E is also a polar vector, but a vector such as B, which may be
written as the product of two polar vectors, is unchanged on inversion and is
called an axial vector. Thus the scalar product E.B is antisymmetric with re-
spect to inversion and is called a pseudoscalar. The expression 5.30 is a true
scalar and will be employed in Chapter 6, where the electromagnetic field is
considered in more detail.

5.5 Gauge transformations

The electromagnetic field vectors B and E may be determined from the poten-
tials A and ¢ by Equations 5.20 and 5.21. However, since it is Band E that de-
termine physically observable phenomena such as the force on a charged
particle (Equations 5.19), it is pertinent to ask to what extent A and ¢ are
determined by B and E. It will be seen that there is some freedom in the choice
of these potentials and this may be attributed to the fact that integration of
Equation 5.20 or Equation 5.21 introduces an arbitrary integration constant.
Let A and ¢ be replaced by some new potentials given by:

A’ =A-YVf; ¢ = ¢+(df/ar), (5.31)

where f is any scalar function of position and time coordinates. Substitution
into Equation 5.20 gives the magnetic field associated with A’:

where the fact (Equation 2.70) that the curl of a gradient vanishes has been
used. The electric field corresponding to ¢’ and A’ may be obtained from
Equation 5.21:
The Interaction of Charged Particles with Fields 71
E’
—V¢' — (0A'/dt)
—V$—V(df]at) — (@A/dt) + (AVs/dt) = E. (5.33)
Thus the potentials are not uniquely defined, since the electric and magnetic
fields are unaltered by the transformation of the potentials described by Equa-
tions 5.31; such a transformation is called a gauge transformation.
It is clear that a change of gauge must not affect the equations describing
physical phenomena and that these must be gauge invariant. For instance, we
might enquire what happens to the Lagrangian (Equation 5.8) under the gauge
transformation (Equations 5.31). Substitution shows immediately that the
Lagrangian is modified by the addition of:

— qu(Vf) — q(af/at) = — q(df/de), (5.34)

since f is a function of r and t. However, these extra terms do not affect the
predictions made using the Lagrangian, since it was seen in Section 3.3 that
the equations of motion are unaltered by the addition of a total time deriva-
tive to the Lagrangian.
The choice of the potentials is arbitrary to the extent that the scalar fin
Equations 5.31 may be chosen, and this freedom can be used to simplify the
equations that arise. Two different gauges are commonly used, the first being
the Coulomb or radiation gauge in which fis chosen so that the divergence of
the vector potential vanishes:
V.A = 0. (5.35)
In the Lorentz gauge, however, the condition imposed is that:

V.A + (0¢/dt)/c? = 0. (5.36)

The latter has the advantage of being a relativistically invariant condition, as

can be seen by noting that the left-hand side of Equation 5.36 is the scalar
product of two four-vectors with components (0/d7,) and Aq. In steady state
problems the two gauges are identical and, in addition, there is no advantage
in using the Lorentz condition, if a non-relativistic approximation is being con-
sidered. Even the application of a condition such as Equation 5.35 or Equation
5.36 does not remove the arbitrariness of f completely, but we would gain
nothing by restricting it further at present.
In the special case of uniform fields, that is fields that are the same at all
points in space and time, particularly simple expressions for the potentials may
be used. If they are written as:

NAD e @ = —Er, (5.37)

72 Advanced Molecular Quantum Mechanics

where B and E are both constant vectors, substitution in Equations 5.20 and
5.21 and the use of vector relations from Chapter 2 shows that the correspond-
ing fields are just B and E:

—V¢—(dA/dt) = V(E.r) = E (5.38)

and
V,A = 3V, (Ban = B. (5.39)
These potentials satisfy both the Coulomb and the Lorentz conditions.
Equation 5.12 gives the energy of a slow-moving charged particle in an
electromagnetic field. However, it is expressed in terms of the potentials rather
than the fields. For uniform fields the potentials (Equations 5.37) may be sub-
stituted. Here we confine our attention to the term involving the magnetic
potential which may be expanded as follows:

(p—qA)’/2m = (p?—2qp.A + q°.A*)/2m

tq’ A’)/2m.
= (p’—qp.Byr (5.40)
The second term in parentheses may be written as:

— (q/2m)Bx , p = — (q/2m)B1 = —w.B, (5.41)

where | is the angular momentum of the particle and p is the associated mag-
netic moment. This term represents the energy of the interaction between
the magnetic field and a magnetic moment u = (g/2m)l.

5.6 Maxwell’s equations

Equations 5.20 and 5.21 relate the electromagnetic fields to the potentials:

B= V,A; E = —V¢—(0A/dt). (5.42)

However, the potentials may readily be eliminated from these expressions to
give equations involving only the fields.
If we operate on both sides of the first of Equations 5.42 with the diver-
gence operator and use the fact (Equation 2.71) that the divergence of a curl
vanishes, the result is:
V.B = V(V,A) = 0. (5.43)
In Section 2.9 it was seen that the divergence of a vector represents a loss per
unit volume. Indeed, if V.B is integrated over a finite volume, we have from
Equation 5.43 and Gauss’ theorem (Equation 2.57):

J V.Bdr = fB.ds = 0, (5.44)

The Interaction of Charged Particles with Fields V3
where the second integral is over the surface bounding the volume. Thus the
flux of the vector B through a closed surface must vanish. This result is related
to the non-existence of magnetic monopoles; the divergence of the electric
vector E will be seen to be non-zero, since isolated electric charges do exist.
The potentials are eliminated from the second of Equations 5.42 by taking
the curl of both sides, noting that the curl of a gradient is zero (Equation 2.70)
and using the fact that the operators V and (0/dt) commute:

Vj E = —V,(V¢)—a(V , A)/at = — dB/at. (5.45)

Integrating over a surface gives:

SV, Eds = $E.dr = — a(f B.ds)/ar, (5.46)

where Stokes’ theorem (Equation 2.63) has been used. This equation shows
that the circulation of the electric vector E round a closed contour is minus
the partial time derivative of the magnetic flux through the contour. Equation
5.45 is thus the induction law that relates the electromotive force in a circuit
to the change in the magnetic flux through the circuit.
The equations:
V.B = 0 (5.47)
and
V,E = — oB/at (5.48)

may be written as one equation by using four-tensor notation:

Fup , Foy , Fra _ 9 aa

Ory lan Org
where the Fyg are components of the electromagnetic field tensor (Equation
5.26) and ry, is a component of the position four-vector. Since the four-tensor
is antisymmetric, the left-hand side of Equation 5.49 vanishes if any pair of
the subscripts aBy are the same. When a®y correspond to the three space com-
ponents, Equation 5.49 reduces to Equation 5.47, while Equation 5.48 arises
when one of the aBy corresponds to the time component. Writing Equations
5.47 and 5.48 in terms of a four-tensor /'yg and a four-vector (0/dr_.) demon-
strates immediately that they are both Lorentz invariant, since the left-hand
side of Equation 5.49 is just a third rank four-tensor. This can be checked ex-
plicitly for the transformation between the frames illustrated in Fig. 4.1 by
using Equations 4.46 and 5.27; each of Equations 5.47 and 5.48 transforms
into a different linear combination of the corresponding equations in the new
frame.
Equations 5.47 and 5.48 cannot completely specify an electromagnetic field,
74 Advanced Molecular Quantum Mechanics

since for example they do not indicate how E depends on time. In fact, these
are just two of the four Maxwell’s equations, which are required for complete
specification of a field. The other pair of equations cannot be derived from the
theory that has been developed so far and it is necessary to go back to the ac-
tion integral and add terms for the field itself; up till now the action integral
has only included terms for a charged particle and for its interaction with an
electromagnetic field. Toavoida major diversion, the derivation of these equa-
tions is postponed until the next chapter, but they are quoted here for the
sake of completeness, and because one of the equations is needed in the next
section.
The second pair of Maxwell’s equations is:

VEO = ples (5.50)

and
V,B = c?[j/eo+ (E/2t)), (5.51)
where €o is the permittivity of free space and has the dimensions M'L°77A? in
the SI system. The other new symbols p, the charge density, and j, the current
density, are functions of space and time, and have dimensions L°TA and LA,
respectively. Since p is the charge per unit volume and j is the flow of charge
per unit time per unit area across a surface, it is not surprising that a four-vector
can be constructed with the components of j as the spatial components and
icp as the time component; this current four-vector with components /, is dis-
cussed in more detail in Chapter 6. The pair of equations can thus be written
as One using four-tensor notation:

(OF o¢/0rg) = jalc*€o, (5.52)

as may easily be checked by substitution of Equation 5.26. Again we note that
Equation 5.52 must be invariant to Lorentz transformations, since it is written
in terms of four-tensors alone.
The integral form of Equation 5.50 may be obtained using Gauss’ theorem
(Equation 2.57):
SE.ds = f (o/€9)dr. (5.53)
This equation is called Gauss’ law and shows that the flux of E through a closed
surface is proportional to the total charge enclosed by the surface; unlike the
divergence of B, the divergence of E does not vanish, since isolated electric
charges do exist.
By using Stokes’ theorem (Equation 2.62) the integral form of Equation
5.51 is:
$B.dr = fc? [j/eo+ (E/82)].ds, (5.54)
The Interaction of Charged Particles with Fields as
showing that the circulation of B round a closed contour is related to a current
through any surface bounded by the contour, this current being made up of
the true current and the so-called displacement current, which involves (dE/0¢)
and which must be included when time-dependent fields are considered.
The four Maxwell’s equations are thus:

V.B = 0
|OFop
,Woy , Fre _ og,
VAE = —(0B/at)) %y %a rg
(5.55)
praia |OF iol Ten
V,B = c?[j/eot+ (0E/30)]) 8 — €0e”
In the mixed system of units these equations are modified by the replacement
of B by B/cand €g by 1/47, but of course the dimensions of all the quantities
involved are also altered.
Finally, we should note that the permeability of free space uo often appears
in electromagnetic equations, but it is related to the permittivity of free space
€9 by Uo€o = c ”, so that equations may be written in terms of Mo, €o or both.
The quantity Uo has the fixed value of 4m X 10°? kg ms 7A ’ in the SI system,
so that € 9is uncertain to the extent that there is an experimental uncertainty
associated with the value of the velocity of light c. Of course use of Wo instead
of €9 or vice versa can introduce factors of c, for which special relativity is not
responsible.

5.7 The potentials and fields due to a stationary charge

The space surrounding an isolated point charge q has spherical symmetry. This
means that ata pointr relative to the charge as origin the vectors B and E must
be along the radius vector r. In addition, the magnitude of the fields can only
depend on the distance from the charge.
Although Gauss’ law (Equation 5.50) has not yet been derived, it should be
familiar to the reader and may be used in its integral form (Equation 5.53) to
obtain the magnitude F of the electric field at a distance r from the charge.
By considering a sphere of radius r centred at the charge, the surface integral
on the left-hand side of Equation 5.53 becomes:

SE.ds = 4n7°E, (5.56)

since E is everywhere perpendicular to the surface of the sphere; the volume
integral on the right-hand side of Equation 5.53 is just:

S (p/eo)dt = Q/éo. (5.57)

76 Advanced Molecular Quantum Mechanics

Equating these two expressions gives:

E = q/4neor’, (5.58)
and, since the direction of the field is along r:

E = qr/4ne€or’. (5.59)
The electric field is given in terms of the potentials by Equation 5.21:

E = —V¢-—(0A/dt) = — V9, (5.60)

since the charge is stationary and the magnetic vector potential A must be
independent of time. When it is recalled that V(1/r) is equal to — r/r* (Equa-
tion 2.78), it is seen that an appropriate scalar potential is:

@ = q/4neor. (5.61)

To obtain the magnetic field B the same arguments may be employed ex-
cept that Equation 5.47 is used instead of Gauss’ law. It is immediately appar-
ent that the magnetic field is zero, and that the magnetic vector potential A
may be taken to be zero also.

5.8 The potentials due to a moving charge

From the previous section we know that, in the rest frame K “ofa charge q,
the potentials at a distance r’ from the charge are given by:

Aa 0; @ = q/4neor’. (5.62)
The potentials in a frame K, in which the charge is moving, may be obtained
by performing a Lorentz transformation, since A‘, A, A, and i¢’/c are the
components of the potential four-vector. If the velocity of the particle in K is
u in the x direction, Equation 4.46 gives:

A, V4,
+ubiG)., | Ay ae A.
(5.63)
a7= A; ¢ = y(uA,+¢’),
where y = (1 — u/c?) 7, or substituting Equations 5.62 and generalizing to a
particle moving with velocity u:

A = yqu/4negc’r’ = ud/c?; @ = yq/4neor’. (5.64)

In their present form these expressions are unacceptable, since they involve 7’,
the distance between the charge and the observer in the K’ frame. Two methods
will be given to express the potentials in terms of quantities measured in the
K frame.
The Interaction of Charged Particles with Fields ay,

For a potential to be experienced by an observer a signal must be emitted

by the charge at some earlier time and this signal is propagated with velocity c.
Let us assume that the frames coincide at t= ¢’ = 0 and that the observer is
situated at the origin of the K frame. The charge is taken to be at position r’ in
its own rest frame and at r in the K frame; r is clearly time dependent. If the
potentials are observed at ¢= rt’ = 0, the signal must have left the charge at
times:
t = —7/c; t' = —r'Ic, (5.65)
where r is measured at the time the signal is emitted. Now, for the emission of
the signal, t’ may be related to r and ¢ by the inverse of the Lorentz transform-
ation (Equations 4.21):
t = 4[¢—(us)/e’]; (5.66)
so that:
,
r = y[r+(u4)/c]. (5.67)

Finally, substitution in Equations 5.64 gives:

A = ud/c?; @ = q/4neo[r + (ur)/c]. (5.68)

Although these potentials have been established for a specific situation, they
apply generally if r is interpreted as the position of the charge relative to the
observer (in the previous section r was the position of the observer relative to
the charge). The important thing to note is that the expressions 5.68, which
are known as the Liénard-Wiechert potentials, must be evaluated at the time
the signal leaves the charge. The potentials are thus expressed in terms of the
so-called retarded values of r and u. Clearly the observed potentials only de-
pend on the instantaneous velocity and position of the particle at the retarded
time, the time at which the signal is emitted by the charge, so that Equations
5.68 apply to a charge moving in an arbitrary manner. The retarded potentials
may be expressed in terms of non-retarded quantities provided that there is
sufficient information about the motion of the particle. This is fairly simple
for a uniformly moving charge, but rather than do this here another method
is presented, in which the retardation effect is automatically accounted for.
Retarded potentials arose because the event to which the Lorentz trans-
formation 5.66 applies is the emission of the signal from the charge and the
relative velocity of the two frames must be taken as the charge’s velocity at
this event. However, if the charge is moving with constant velocity, the same
rest frame K’ for the charge is appropriate at both the emission of the signal
and the observation of the potentials. The position r’ of the charge in K’ may
be evaluated in terms of r at any time, and here the time of observation t =
t' = Oischosen. The inverse of the transformation (Equations 4.21) then gives:
78 Advanced Molecular Quantum Mechanics

r= rt+(y—1)(unu/v’, (5.69)
from which it is easy to show that:

fa= Alte (u.r)?y?/e?P]?. (5.70)

Substitution in Equations 5.64 gives finally:
A = udjc’; @ = (yq/4neor)[1 + (un?yle?P7]2. (5.71)
Again these are general expressions if r is taken to be the position of the charge
relative to the observer. It must be emphasized that Equations 5.71 only apply
to a charged particle moving at constant velocity and that the potentials are to
be evaluated at the time of observation, since the Lorentz transformation 5.69
applies to the event of observation.
For charges moving with velocities much less than the speed of light it is
convenient to expand the potentials (Equations 5.71) as power series in (u/c)
and to neglect terms of order higher than quadratic. When this is done, we
obtain:
A = (q/4n€ocr)[u/e + O((u/c)*));
5.72)
@ = (q/4neor)[1 + u?/2c? — (u.r)?/2c?r? + O((u/c)*)) .
In their present form these potentials satisfy the Lorentz gauge condition
(Equation 5.36) to the required order. (In working out the divergence of A it’
should be remembered that r is the position of the charge relative to the ob-
server and that it is the divergence at the observer that is required; in addition,
the position of the observer is fixed and only the charge’s position depends
explicitly on time.) However, when a non-relativistic approximation is being
considered, it is more convenient to work in the Coulomb gauge, in which the
divergence of A vanishes (Equation 5.35). This may be achieved by perform-
ing a gauge transformation (Equations 5.31) with g(u.r)/2c’r as the scalar f.
The transformed potentials are then:

A = (q/8n€cr)[u/e + (ur)r/r’c + O((u/c)?)];

(5.73)
% = (q/4neor)[1 + O((u/c)*)],
and these may readily be shown to satisfy the Coulomb gauge condition.
These potentials are used in the next section, where the Hamiltonian for
two charged particles is obtained. Since we will eventually be considering the
motion of electrons in molecules, it might be thought that the result, Equations
5.73, is not appropriate, since the charge is assumed to have constant velocity.
However, to order (u/c)? the same result is obtained if the Liénard-Wiechert
potentials for an arbitrarily moving charge are used and these retarded expres-
The Interaction of Charged Particles with Fields Sis)

sions are rewritten in terms of quantities measured at the time of observation.

To do this a knowledge of the particle’s acceleration is necessary, but as first
shown by Darwin the acceleration does not make a contribution to the poten-
tials in the order considered here.

5.9 The interaction of two charged particles

The Lagrangian for an isolated particle with charge q,, mass m, and velocity
u, in the presence of electromagnetic potentials A and ¢ is given by Equation
5.8 as:
£L = —mc(1 —u3/c?)? + qyA.u,
— 419. (5.74)
For the remainder of this section it will be assumed that u, <c. If the poten-
tials at r,, the position of this particle, are entirely due to a second slow-moving
particle distinguished from the first by the subscript 2, then they are given by
Equations 5.73:
A (q2/8m€9cr) [ug/¢ + (u2.r)r/r°c =F O((u2/c)*)];
(5.75)
= (q2/4meor)[1 + O((u2/c)*)],
where r= (1.— r,) is the position of electron 2 relative to electron 1. Substi-
tution in Equation 5.74 gives:

f= m,c*(1 = ur/c)? +(q 192/87 or) [(uy .u2)/c?

+ (u,.r)(up.r)/c?r? — 2 + O((u/c)*)] (5.76)

as the Lagrangian for particle 1.
Now addition of a term such as — m,c?(1 — u3/c?)? to this Lagrangian can-
not affect the equations of motion for particle 1, since it is independent of
r, and uy. The Lagrangian for particle 1 subject to potentials due to particle 2,
the motion of which is assumed to be known, can thus be written:

C=—mcd — u3/c?)i — mc?(1 — u3/c?)?

Ee (4142/87€0r) [(u1.U2)/c? + (u;,.r)(U, Sige

=" a2 O((u/c)*)). (5.77)

However, this Lagrangian is symmetric to interchange of the subscripts 1 and

2, so it must also be an appropriate Lagrangian for particle 2 moving under
the influence of potentials due to particle 1. It must be concluded that Equa-
tion 5.77 is the Lagrangian for the whole system, particle 1 plus particle 2. For
consistency the first two terms should also be expanded as power series in
(u/c), but it is appropriate to retain terms of order mc?(u/c)*; this is because
80 Advanced Molecular Quantum Mechanics

these results are to be applied to molecular problems and in the ground state
of the hydrogen atom, for example, (q¢1q2/87€or) is of the order of me?(u/c)?
(see Section 8.7). Thus:

L= LY [—myec? + pm? + mu}/8c?] + (q1q2/87€

i=1,2
or)[(u.u2)/c?
+ (u,.r)(uy.r)/c?r? — 2] + O(c? (u/c)?). (5.78)
Now that we have a Lagrangian for the system the corresponding Hamil-
tonian may be found by the usual prescription. From Equation 3.24 the mo-
mentum of particle 1 is:

pi = 0£/du; = my, + myuyuj/2c? + (4142/87 ocr) [U2/c

+ r(uz.1)/cr?] + O(me(u/c)>) (5.79)

with a similar expression for p2, the momentum of particle 2. These equations
may be inverted to give the velocities of the particles in terms of their mo-
menta; for particle 1 successive approximation gives:

uy = pi/my— pipi/2mic? ag 192/87€9m mC") [p./r

+ r(p2.r)/r?] + O(c(p/mc)°) (5.80)

and there is a similar equation for uy. Finally, substitution of these and Equation
5.78 into Equation 3.31 for the Hamiltonian gives:

= ris U;-Pj — Af

lI 2 [mjc? * p; 2m; a D;/8mjc?] + q1q2/4m€or

1=1,2

— (4142/87€9mym2¢”)[(py.0)/r + (pi -1)(t-p2)/r?]

+ O(mc?(p/mc)°). (5.81)
This then is the Hamiltonian for two charged particles and, as we saw in Sec-
tion 5.2, it may be generalized to include external electromagnetic fields by the
following replacements:

Piri = Dae aA
(5.82)
>I PP Gidi,
1=1,2

where A; and ¢; are the external potentials at particle 7. This result will be used
in Chapter 9 when the quantum mechanical theory for two electrons is con-
sidered.
The Interaction of Charged Particles with Fields 8]

5.10 The Thomas precession

The concept ofelectron spin was first introduced to account for fine structure
in atomic spectra. It was postulated that the electron has an intrinsic angular
momentum fs and an associated magnetic moment uw = — (eh/m)s, where — e
and m are the charge and mass of the electron; in a magnetic field the energy
associated with this moment is —y.B. However, a discrepancy soon became
apparent, since an electron moving with velocity u (<c) under the influence
of an electric field E, should according to Equations 5.29 experience a mag-
netic field:
B = (E,u)/c’ (5.83)

in its own rest frame. The energy of interaction between the spin magnetic
moment of the electron and this magnetic field should thus be — w(E , u)/c’,
but in atoms where the electric field is provided by the nucleus experiment
showed that this expression was a factor of two too large. This discrepancy
can be explained in terms of a relativistic effect, if the concept of spin is ac-
cepted, and this may be done without considering quantum mechanics.
To do this the concept of precession must be introduced. In a magnetic
field B an electron experiences a torque u , B by virtue of its intrinsic magnetic
moment pw. Now this torque will change the angular momentum of the electron
and the rate of change of the angular momentum is just equal to the torque:

d(hs)/dt = u ,B = —(eh/m)(sp B). (5.84)

Thus the change in the angular momentum is perpendicular to itself and the
magnetic field, so that the magnitude of the angular momentum vector and
the angle @ that it makes with the magnetic field vector do not change, but
instead the angular momentum precesses about the direction of B (Fig. 5.1).
The angular velocity w, of this so-called Larmor precession is in the same di-
rection as B and its magnitude may be found by considering a short time df,
in which the precession angle d@ is w,dt. This angle is given also by:

dd = d(hs)/hs sin 0 = eBdt/m, (5.85)

where Equation 5.84 has been used, so that:

O77. — eB/m. (5.86)

All this is analogous to the precession of a gyroscope ina gravitational field.

The important thing to note is that the Larmor frequency w,/2n is directly
proportional to the energy of the interaction of the electron’s spin magnetic
moment with the magnetic field and that the two may be thought to be inter-
related.
82 Advanced Molecular Quantum Mechanics

As

Che

Fig. 5.1. The precession of the angular momentum of the electron about the
direction of the magnetic field.

Let us now consider an electron moving with velocity u along the x axis of
an inertial frame K in which there is an electric field E directed along the y
axis. In the rest frame of the electron the precession will have an angular vel-
ocity about the z axis of:
pe eUlinic., (5.87)
where Equations 5.83 and 5.86 have been used. Now by virtue of its charge
the electron will experience a force due to the electric field and will suffer a
resulting acceleration:
@ = —eH/m. (5.88)

in the y direction. It will be seen that as a result of this acceleration the axes
of the rest frame of the electron appear to be themselves precessing when
viewed from the frame K.
After a short time dt the situation will be as in Fig. 5.2. The rest frame K”
of the electron is moving with velocity u' = adt in the y’ direction relative to
a frame K’, which is itself moving with velocity wu in the x direction relative to
the K frame; the frames are assumed to be coincident at t=O andu' <u <c.
Use of Equations 4.28 and 4.29 shows that the velocity v of the K” frame rela-
tive to the K frame has components:

Vy = U; vy = u/ylu), (5.89)
where y(u) = (1 —u?/c?)
u“/c*) 2.
?. On On the
the other
other h hand the velocity
ity v v" of theK frame
relative to the rest frame of the electron has components:
 The Interaction of Charged Particles with Fields 83

Fig. 5.2. The relationship between the inertial frames K, K’ and K”.

y= =alyGi): Vay! (5.90)

Now the principle of relativity tells us that v should be equal and opposite to
v’. Equations 5.89 and 5.90 show that their magnitudes are equal but that
their directions are not, since:

9 =~ tand = v,/v, = u'/uy(u);

(5.91)
Q”
R tan 0” = vyfv = u'y(u’)/u.
This means that for the principle of relativity to be obeyed the K” axis system
must be rotated through an angle:

dd = 6-6" ~ Ww jw[1y@—yw’)| ~ —uu'/2c’, (5.92)

where the assumption that u’ <u <c has been used. Substitution of u’ = adt
and Equation 5.88 shows that the K” axes precess with angular velocity:
wp = + euE/2mc’, (5.93)
when observed from the K frame; this is the Thomas precession. Thus the pre-
cession rate of the spin angular momentum in the K frame is:

= Oy + Op = — eu) 2c; (5.94)

just half its magnitude in the rest frame of the electron (Equation 5.87).
84 Advanced Molecular Quantum Mechanics

Since the energy of interaction between a magnetic field and the spin mag-
netic moment of the electron is directly proportional to the angular velocity
of precession, we conclude that, when the magnetic field is due to the motion
of an electron relative to a frame in which there is an electric field, special
relativity introduces a correction factor of ;; the energy of interaction is thus
—u.(E , u)/2c? and this is just the spin-orbit interaction term when the elec-
tric field arises from a nucleus. Later it will be seen that this correction factor
arises naturally from the Dirac equation, which is a relativistic quantum mech-
anical equation for the electron.

Bibliography

Electromagnetism
Coulson, C. A. (1948), Electricity, Oliver and Boyd, Edinburgh.
Feynman, Leighton and Sands: Volume II.
Landau and Lifschitz: Chapters 3, 4 and 5.
Jackson, J. D. (1962), Classical Electrodynamics, Wiley, New York.
Panofsky, W. K. H., and Phillips, M. (1962), Classical Electricity and Magnet-
ism, Addison-Wesley, Reading, Mass.
Rindler, W. (1966), Special Relativity, Oliver and Boyd, Edinburgh: Chapter 6.

The interaction of charged particles

Darwin, C. G. (1920), ‘The dynamical motions of charged particles’, Phil. Mag.,
39, 537: a relativistic treatment of the motion of two interacting, charged
particles.
Landau and Lifschitz: Chapter 8.

The Thomas precession

Thomas, L. H. (1926), ‘The motion of the spinning electron’, Nature, 117, 514:
the original explanation of the discrepancy between theory and experiment
for the spin-orbit coupling in atoms.
Eisberg, R. M. (1961), Fundamentals of Modern Physics, Wiley, New York:
pages 340-344.
Hameka: pages 45-49.
CHAPTER SIX

The Classical Theory of Electromagnetic

Fields

The classical field theory that is developed here is not used until Chapter 12,
where its quantization is considered. Consequently, a reading of this chapter
may be delayed until then, provided that the validity of Gauss’ law (Equation
5.50) is accepted; it is recalled that the proof of this equation, which is used
in Section 5.7, was postponed until this chapter, together with the proof of
Equation 5.51.
The reason for this postponement was that, although the Lagrangian for a
charged particle subject to an electromagnetic field had been obtained, the
Lagrangian for the field itself had not. There is clearly a fundamental differ-
ence between a particle, which is concentrated at a point, and a field, which
is spread out through space. The Lagrangian for a particle is a function of its
position and velocity, while for the Lagrangian of a field some new variables,
which are themselves functions of position r and time ¢, are necessary. This
means that our ideas about Lagrangians, Hamiltonians and equations of motion
will need some modification, when a continuous, rather than a discrete, system
is under consideration. To see how the theory needs to be modified we first
discuss the mechanics of a continuous system.

6.1 Continuous mechanical systems

Let us consider a one-dimensional system consisting of an infinite chain of

identical particles. A continuous system may be obtained by making the separ-
ation between neighbouring particles infinitesimally small; the generalization
to a three-dimensional system is trivial.
It is assumed that the particles are of mass m and are joined to their

85
86 Advanced Molecular Quantum Mechanics

neighbours by ‘springs’ of equal length a and with equal ‘force constants’ k.

The Lagrangian for the system is the difference of the total kinetic energy and
the total potential energy (Section 3.4):

£= Dalmni— Knin — 1i)’1, (6.1)

where 7; is the displacement of the ith particle from its equilibrium position,
n; isits velocity and end effects have been neglected. This is just the Lagrangian
for coupled oscillators and may be rewritten as:

£ = & pal(mlayni— ka(nier — 03)/a)"). (6.2)

To go from this discrete situation to a continuous system the separation a
between the particles is replaced by the infinitesimal dx and the summation
becomes an integration. At the same time (m/a) becomes the linear mass den-
sity u, ka is replaced by the Young’s modulus Y and (n;,,; — n;)/a is interpreted
as (0n/dx). The Lagrangian for the continuous system is thus:

where L is the Lagrangian density, which in the present example is:

L = $[un?— Y(an/ax)’). (6.4)

The variable n(x, f) may be thought of as a generalized coordinate similar to
q in Chapter 3, except that it is a function of position as well as time. The
quantity 7 is just the partial derivative of n with respect to time.
To obtain the equation of motion from this Lagrangian the method of Sec-
tion 3.3 is used, that is 7 is varied so that the action integral between times
t, and ty, is minimized:

5S = 5 f° £(n,n, dniax)dt = 0. (6.5)

a

Here it is assumed that the Lagrangian does not depend explicitly on time,
and that 6n, the change in n, is zero att, and t,and also at the limits of the
space integration in Equation 6.3. Substitution of Equation 6.3 in Equation
6.5, expansion and integration by parts gives:
lo
65 = 8| |L(n, i, an/ax)dxae

~
OL OL OL F)
ll —— 6n +—6n+——— 6 (—
pee” E ay SPRCOnan)e aney ee
The Classical Theory of Electromagnetic Fields 87

_ ee)
ple p[ae_a fat)_a/
Syuatlenl
a Vi.
Parl aOnen Co
where the integrated parts have been omitted, since they vanish as a result of
the assumed boundary conditions. Now 5S must vanish for an arbitrary choice
of 5n, so that:

ab afar) _a/_a_)_, Be
dn at\dn} ax\a(an/ax)) ee)
This is the equation of motion, which is to be compared with Equation 3.6 for
a discrete system.
For the example used here, substitution of the Lagrangian density (Equa-
tion 6.4) in Equation 6.7 gives:

Y(0?n/dx?)— u(8?n/dt?) = 0, (6.8)

which is just the one-dimensional wave equation for compressional waves
travelling with velocity (Y/uP.
The definitions of the momentum (Equation 3.24) and the Hamiltonian
(Equation 3.33) for a discrete system may readily be extended to the continu-
ous case. The canonical momentum density conjugate to 7 is thus:

p = (AL/dn), (6.9)
while the Hamiltonian density is:

H = np—L. (6.10)
In our example the momentum density is just un and the Hamiltonian density,
which is given by:
H = 3[un? + Y@n/dx)’], (6.11)
is clearly the sum of kinetic energy and potential energy densities.
So far attention has been confined to a one-dimensional system, but the
extension to three dimensions is trivial. Remembering that the subscript 7 can
be x, y or z and that the repeated subscript summation convention is being
used, Equation 6.7 generalizes to:

al_afal\ a =the ees 64%)

dn odt\dn) ar; \d(dn/dr;)

where 7 is now a function of the position vector r and the time f; by using
four-vector notation this equation may be written in a more abbreviated form:
88 Advanced Molecular Quantum Mechanics

aaa 20. (6.13)

8n Oy \0(0N/ Ore.)

This equation is Lorentz invariant provided L is a scalar density, that is if L is

itself Lorentz invariant; this restriction is quite severe and is useful in choosing
Lagrangian densities. The definitions of the momentum and Hamiltonian den-
sities are unaltered in the three-dimensional case.
In Section 3.5 constants of motion were found for a system of particles by
considering the derivative of the Lagrangian with respect to space and time
coordinates. A similar approach is possible for continuous systems. Here we
consider 0L/dr,, the derivative of the Lagrangian density with respect to a
component of the position four-vector. Since L is a function of n and its
derivatives 0n/0r,, we may write:

ab_
Ore (_2L_) (a@=nlarg) )
(an) ,i
(2) l (6.14)

Use of the equation of motion (Equation 6.13) and the fact that 0(0n/0rg)/drq
is the same as 0(07/0r,,)/0rg now shows that:

OL 1 0y/ SY OLaA pan One (amor ee

re Org eit Ore 0(0n/drg) Org

_ Org}a (fan) (az

\Ora} \8(8n/drg))| i
Fi
Since (0L/0r,.) can be expressed as 6y¢(0L/drg), this equation may be rewritten
as:
(OT 4g/drg) = 0, (6.16)
where the components of the four-tensor are given by:

on OL
Leg = Soph a= lee
eh! fa | sod)
It should be noted that the Tyg are not uniquely determined by Equation 6.16,
since its validityisunaffectedif dU ggy/dry is added to Tyg, where Uggy is any
tensor antisymmetric in the subscripts B and ¥.
Equation 6.16 may be put in a more useful form by interpreting the left-
hand side as the four-divergence of a four-vector TJ with components Tyg. It
can then be rewritten as:

(07, ,/0t) = —icV.T,, (6.18)

The Classical Theory of Electromagnetic Fields 89

so that the time derivative of the integral of Tq4 over all space is:

0
apt Lead? = f (07x, /dt)dt

ll =I) Veer

ic {FT ..ds) (6.19)

where Gauss’ theorem (Equation 2.57) has been used. If it is assumed that
and its derivatives vanish at infinity, then so do the components of T, and the
surface integral on the right-hand side of Equation 6.19 vanishes. Thus f Ty 447,
the integral of 7, over all space, is a constant in time and we may define the
four-vector:
Gy = k fTy,dt = constant, (6.20)

k being an arbitrary constant.

The time component of the four-vector (Equation 6.20) may be expanded
using Equation 6.17:

Gg = kf Tagdt = k f [L — (0n/0t)(0L/0(0n/dt))|
dr. (6.21)
Equations 6.9 and 6.10 now show that, if k has the value — i/c:

G4 = (i/ce)
f Hdt = (i/c)K, (6.22)
where # is the Hamiltonian. Thus G, is just the time component of the 4-
momentum, as may be seen by reference to Section 4.7. Consequently the
four-vector:
Ge Cie OT (6.23)

may be interpreted as the four-momentum of the continuous system; the spatial

components represent the momentum and describe the way in which the energy
moves about in the system. The total energy and momentum in all space are
thus conserved, since we have just seen that the four-vector Gg is a constant
of motion. These conclusions are not affected by the fact that the Tyg are not
uniquely defined by Equation 6.17, since the integral of 0Ug4,/0ry over all
space vanishes as may easily be demonstrated using Gauss’ theorem (Equation
20):
Finally, it should be noted that, although the example considered here is
for a continuous mechanical system, the theory applies to any continuous sys-
tem, and in particular it is appropriate to fields. The Equations 6.9, 6.10 and
6.13 are appropriate toa field that is characterized by a scalar variable n, which
is, of course, a function of space and time coordinates; such a field is referred
to as a scalar field. However, there is no reason why a field should not be
90 Advanced Molecular Quantum Mechanics

characterized by more than one variable and, for example, these could be the
components ofa vector. For such a vector field there is an equation of motion
similar to Equation 6.13 for each component of the vector. In addition, there
is a momentum density conjugate to each field variable and the Hamiltonian
density generalizes to:
H = Xm (0L/0n,)
—L, (6.24)

where the subscript 1 distinguishes the field variables. Similar remarks apply
to the tensor Tg and the four-momentum Gq.

6.2 The Lagrangian density for an electromagnetic field

In the last chapter it was seen that an electromagnetic field may be character-
ized by the components Ag of the potential four-vector. These four com-
ponents are functions of position r and time f, and they might be expected to
be appropriate field variables, so that there are four equations of motion (Equa-
tion 6.13) for the field. However, before we can proceed any further an appro-
priate Lagrangian must be found and to do this the action integral is again
considered.
For a system consisting of charged particles and an electromagnetic field
the action integral consists of three parts, one for the particles, one for the
field and one for the interaction between the two. When the equations of mo-
tion of a particle were obtained, only those terms in the Lagrangian which
depend on the position and velocity of the particle were needed; that is the
electromagnetic potentials were regarded as known and an explicit term for
the field was unnecessary. However, in finding the equations of motion for a
field, the potentials are the variables and the motion of the charged particles
is assumed to be known. In this case the action for the particles alone is un-
important, since it is not a function of the field variables. The action due
to the field itself has yet to be derived, but the interaction term is already
known (Equation 5.3), although it will be necessary to devote the next sec-
tion to rewriting it in terms of the current four-vector.
A number of restrictions may be made on the action integral for the field.
In the last section it was seen that the Lagrangian density is a function of the
field variables and their partial derivatives with respect to space and time co-
ordinates (if it were to depend explicitly on time, this would imply that time
is not homogeneous). However, explicit dependence on the potentials them-
selves is not possible, since they are not uniquely determined and the Lagrangian
density must be invariant to gauge transformations. Thus, only quantities of
the type (0A,/drg) are involved, and these are related to the Fug, the com-
ponents of the electromagnetic field tensor (Equation 5.22).
The Classical Theory of Electromagnetic Fields 91

It has also been noted that the Lagrangian density must be an invariant, if
the Lorentzinvariance of the equations of motion is to be ensured. An invariant
(Equation 5.30) has already been constructed from the F yg and this suggests
that for an electromagnetic field alone an appropriate action integral is:

aff FagFagdtdt = 2a ie f (B?— E?/c?)drdt. (6.25)

Before considering the value of the constant a two comments need to be made
about this choice of action integral.
First, the invariant has been chosen to be quadratic in the Ag, although it is
clearly possible to construct invariants that are say quartic in the Ay. The justi-
fication for this choice depends on the experimental fact that electromagnetic
fields may be superimposed, so that the field due to a collection of charges is
just the sum of the fields produced by the charges individually. Thus, for an
equation of motion for the field to be valid it must be possible to construct
new solutions by adding together other solutions. This is only possible if the
equation of motion for the field is a differential equation that is linear in the
field variables Ay. Reference to the equation of motion (Equation 6.13) indi-
cates that for this to be true the Lagrangian density must be quadratic in the
field variables.
Secondly, it was noted in Section 5.4 that E.B is also an invariant quadratic
in the Ay. However, it was pointed out that this is not a true scalar, since it
changes sign on inversion of the coordinate system. In addition, a term pro-
portional to E.B in the Lagrangian does not, in fact, affect the equations of
motion. In Section 3.3 it was seen that the addition of a total time derivative
to a Lagrangian does not affect the equations of motion. The corresponding
result for a Lagrangian density, for which the action is an integral over space
as well as time coordinates, is that the equations of motion are unaffected by
the addition of a term 0F,/0r,, where Fy, is a four-vector. It may be shown
that E.B is a term of this type, since it may be written as:

“) 0A
E.B = (ic/8)€agysFaghys = (ic/2)— |€apysAp — |. (6.26)
Oy, ory

where €ys5 is the unit antisymmetric tensor of rank four analogous to €;;, for
three dimensions; the details are left to the reader.
It remains to choose a value for the constant a in Equation 6.25 and clearly
this will depend on the system of units employed. For the SI system agree-
ment with experiment is obtained by taking a to be — c7€o/4 (= — 1/4 uo),
where €o and Mo are respectively the permittivity and permeability of free
92 Advanced Molecular Quantum Mechanics

space; it may easily be checked that this choice makes the action integral
dimensionally correct. That a@ must be negative is due to the fact that the
quantity (0°A/d¢*) appears with a negative sign in Faghag. However, it must
appear with a positive sign in the action, since it may be made arbitrarily large
by varying the potentials sufficiently rapidly, and if it had a negative sign the
action could not be minimized as required by the principle of least action. The
Lagrangian density for a field is thus:

DP = CeohapFaght = —yeolC
Ba Ee). (6.27)
By substitution of Equation 6.27 in the equations of motion (Equation
6.13) the field equations for free space could now be obtained, but the more
general situation in which electric charges are present is considered after the
Lagrangian density for the interaction of charges with a field has been deter-
mined.

6.3. The current four-vector

The action integral for the interaction of a point charge q with an electromag-
netic field is (Equations 5.3):
f2qA da. (6.28)
Now that the field itself is under consideration, it is desirable to be able to
treat any distribution of charge and not just a single point charge. To do this
the charge density p is introduced. The total charge in a region of space is then
the appropriate volume integral of p, that is f pd7. A point charge q may be
included in this description, since its contribution to the charge density may
be written in terms of a Dirac delta function, g5(r — rq), where r, is the vector
position of the charge.
For an infinitesimal region of space dz the included charge is dg = pdr.
Thus we can write:

dqdrg = pdtdrg = pdrdt(dry/dt) = j,drdt. (6.29)

Now dq isa scalar. so that the left-hand side of this equation is the component
of a four-vector. The same must be true of the right-hand side and, since drdt
is a scalar and unaltered by a Lorentz transformation:

Ja = p(drg/dt), (6.30)
is a component of the so-called current four-vector. The spatial components
of this four-vector can be written as j = pu, where uis the charge velocity at a
The Classical Theory of Electromagnetic Fields 93

particular point, so that j is the flow of charge per unit time per unit area
across a surface; the time component icp is proportional to the charge density.
If the charge q is replaced by the volume integral of the charge density, the
action (Equation 6.28) becomes:

SS pdt Agdra = S72jaAgdrdt,

S (6.31)
where Equation 6.29 has been used. The Lagrangian density for the interaction
between a charge distribution and an electromagnetic field is thus j.4y.

6.4 The second pair of Maxwell’s equations

The results of the two preceding sections show that the Lagrangian density for
an electromagnetic field in the presence of a charge distribution is:

L = jyAg — €€oF
ygF ag/4, (6.32)
where the components of the electromagnetic field tensor are given by:

Fog = (0Ag/drq) — (0A q/0r8). (6.33)

Strictly speaking there should also be a term for the charges themselves, but
this is independent of the field variables A,, and does not affect the field
equations to be derived.
There are four equations of motion for the field, one for each of the com-
ponents A,, and reference to Equation 6.13 shows them to be given by:

Big OS Ol apne, (6.34)

84q Org \8(0Aq/ Org)
Substitution of Equations 6.32 and 6.33 gives:

a) a) 0As OA 0As 0A
jan + (C*e0/4)=—Org \0(0Aq/drg) es Org}4) ea
[\Or, \Ory Ore

ay beige Won fcw

calle 2sOy _ Bs2
Ja 105, |a(BAg/Org)| Ory Ory Ory Ors
=j,+ pees 0Aq A
dA} _ j + ce! F 06) (6.35)
org org Ora Org

Finally, we note that Fog = — Fgq, so that:

(dF yg/Org) = ja/c”€o. (6.36)

94 Advanced Molecular Quantum Mechanics

This is just the second pair of Maxwell’s equations written in four-tensor nota-
tion; it was quoted (Equation 5.52) and interpreted in the last chapter.
For convenience Maxwell’s equations are repeated here in full and abbrevi-
ated form:
V.B =
= 0 | OFap , Fey , WF ya _ . 6.37
(6.37a)
V,jE=—(aB/at)) %y Fa (6.37b)

V.E = p/eéo | OF y iB ies (6.37c)

VB = [ileo+ (0E/ary}/c2} 2% = oe” (6.374)

Itis recalled that the first pair of equations arise from the expressions 5.42 for
the fields in terms of the potentials:

B=V,A; E = —V¢—(0A/20). (6.38)

It can be shown immediately that the second pair of Maxwell’s equations is
consistent with charge conservation by taking the divergence of Equation
6.37d and substituting Equation 6.37c:

V.V ,B = V.j/c?eo+ [A(V-E)/A4]/c?

ll (V.j + dp/d2)/c€o. (6.39)
Now the left-hand side of this equation vanishes, since it is the divergence of a
curl (Equation 2.71), so that:

V.j+dp/at = 0; (6.40)
this is just the charge conservation equation 2.55. This result could have been
obtained using four-tensor notation by operating on the combined equation
for Equations 6.37c and 6.37d with the operator 0/dr,, and summing over the
subscript a (that is taking the four-divergence of Equation 6.36):

(Bja/Ara)lc*€o = (8’Fag/Ararg); (6.41)

the right-hand side of this equation vanishes, since the components Fyg of the
electromagnetic field tensor are antisymmetric, giving:

Ojn/Ory = 0, (6.42)
which is just Equation 6.40 written in terms of four-vectors.
We started this section with the Lagrangian density (Equation 6.32) for an
electromagnetic field in the presence of a charge distribution. The results of
Section 6.1 can be used to obtain the momentum and Hamiltonian of the
The Classical Theory of Electromagnetic Fields 0)

field, and for this it is assumed that no charges are present, that is jg = 0.
The Lagrangian density is then — €7€oF ag agl4 and its derivative with re-
spect to 04,/drg is:

dL /0(0A,/drg) =—4307€o (Fey —F yg) = —c?€oF

gy, (6.43)
where Equation 6.33 has been used. Thus, the components of the tensor
Tyg (Equation 6.17) may be written:

Tag = Sagl — (0A4/dr_)(0L/0(0A

y/drg))

— €7€9 [SagF ysF ys [4 —(0Ay/Ore)F

ey) - (6.44)
This expression may be made symmetric in the subscripts a and B by adding
= c7€9(0A4/0r,)F py to the right-hand side of this equation:

SO c7€o lOaphysl elt Foal oy. (6.45)

This ruse is permissible, since we saw in Section 6.1 that Tg is undetermined

to the extent that a term 0Uyg,/0r, may be added to it, where Ugg, is anti-
symmetric in 6 and y; furthermore, this modification of Tyg does not affect
the total Hamiltonian or momentum of the field.
The Hamiltonian of the field may now be obtained from Equations 6.22
and 6.23:
H = —f Tagdt = c7€p f (FysFys [4 — FayFay)d7

= 3€0 S (c’B?+E”)dr, (6.46)

where explicit substitution for the electromagnetic field tensor (Equation 5.26)
has been made. The components of the momentum G are (Equation 6.23):

G; = — (ic) [T,,dt = —icéo f FF adr, (6.47)

where explicit substitution for the electromagnetic field tensor (Equation 5.26)
B to give:
G = 9 fE,Bdr = c’’ f Sdr, (6.48)
where S = €9¢’E , Bis the so-called Poynting vector.

6.5 Electromagnetic waves

Maxwell’s equations may easily be shown to be consistent with the existence

of electromagnetic waves, and to do this B and E are each separately elimi-
nated from them.
Taking the curl of Equation 6.37d gives:
V (VB) = (Vajleoc” + (OV , E/at)/c?. (6.49)
96 Advanced Molecular Quantum Mechanics

Now the left-hand side is just equal to — V7B from Equation 2.72 and the fact
that V.B vanishes (Equation 6.37a). Substitution of Equation 6.37b for V , E
followed by rearrangement then gives:

VB — (9?B/at2)/c? = —(V pj)/€oc?. (6.50)

An equation in which only E appears may be obtained in a similar fashion by
starting with Equation 6.37b:

VE — (97E/8t?)/c? = Vpleo+ (dj/8t)/€0c’. (6.51)

In the special case of a vacuum j and p both vanish and Equations 6.50 and
6.51 reduce to:

VB —(82B/dt2)/c2? = 0; W?E—(07E/8t?)/c? = 0. (6.52)

These represent six wave equations, one for each of the components of B and
E. In each case the velocity of the wave is just c, the velocity of light. When
charges are present, Equations 6.50 and 6.51 hold and the terms in j and p on
the right-hand sides of these equations are damping terms which represent
energy dissipation.
The wave equations may also be derived using the electromagnetic poten-
tials; for simplicity we confine ourselves to the case of a field in free space. In
Section 5.5 it was seen that there is some freedom in the choice of potentials,
and a gauge transformation (Equation 5.31) can always be applied. Here it is
supposed that the transformation has been chosen so that the scalar potential
@ vanishes everywhere. The electromagnetic fields (Equation 6.38) are then
given by:
. B= V,A; E = —(0A/d2). (6.53)
When these expressions are substituted into Equation 6.37d withj set equal to
zero, we obtain:
V\(V , A) = — (07A/dt7)/c?, (6.54)
and after use of Equation 2.72 and rearrangement, this becomes

V7A — V(V.A) — (07A/dt?)/c? = 0. (6.55)

Now, although one condition has already been imposed on the potentials
by insisting that @ is zero everywhere, the vector potential A is not completely
determined and a further condition may be imposed. It is recalled that under
a gauge transformation (Equation 5.31):

A’ = A-Yf: d = $+ (af/at), (6.56)

so that if the scalar f is chosen to be time-independent the scalar potential
The Classical Theory of Electromagnetic Fields o7

remains zero. Consequently, the gradient of any function of position may be

subtracted from the vector potential and, by choosing f so that V?f=V.A
everywhere, the vector potential may be chosen to satisfy the Coulomb gauge
condition (Equation 5.35), V.A’ = 0. Of course, fmust be time-independent,
so that V.A must be also for this choice to be possible. However, Equations
6.37c and 6.53 show that in free space (p = 0):

V.E = 0 = —av.A)/ar, (6.57)

showing that V.A is indeed time-independent. Now that the potentials are fixed
the primes may be dropped, so that the conditions satisfied by the potentials
are:
V.A = 0; ¢ = 0. (6.58)

It is noted that these potentials also satisfy the Lorentz gauge condition (Equa-
tion 5.36).
Since the vector potential has been chosen to be divergenceless, Equation
6.55 reduces to:
V*A — (07A/0t7)/c? = 0. (6.59)
Again we have a wave equation, this time with the vector potential as variable.
The wave equations 6.52 for B and E in free space may be recovered from
Equation 6.59 by operating on it with V , and 0/df, respectively, and using
Equations 6.53. However, it is the wave equation for A that is used in the next
section.

6.6 Solution of the wave equation for free space

The wave equation 6.59 represents three equations, one for each component
of the vector potential A. The general solution of one of these equations is:

A, = fk —wt), (6.60)
where f is any function of (k.r — wt) and w is an arbitrary constant, while the
arbitrary wave vector k is restricted in that its magnitude has the value w/c;
these assertions may be checked by direct substitution of Equation 6.60 in
Equation 6.59. Of course, boundary and other conditions may be used to re-
strict the solution 6.60, but first it is convenient to write it in an alternative
form and this is done by solving Equation 6.59 by a different method.
Equation 6.59 is solved by the separation of variables method by substitut-
ing:
A(r, t) = q(AQ), (6.61)
98 Advanced Molecular Quantum Mechanics

to give two differential equations, one for q(t) and one for the components of
A(r):
d’q/dt? + w*q = 0; V7A + (w/c7)A = 0, (6.62)

where w is a constant. The solutions of these equations are:

q(t) = q(O) exp (—iwt); A(r) = A eexp (ik.r), (6.63)

where q(0), A, w and k are arbitrary except that the magnitude of k is restrict-
ed to w/c; in addition, if A(r, 4) is to be finite for all values of r and ¢, both k
and w must be real.
In Equations 6.63 e is a unit vector, which is called the polarization vector
and which can only be perpendicular to the wave vector k. This restriction
arises because A(r, f) is to satisfy the Coulomb gauge condition (Equation
6.58), so that A(r) must be divergenceless. Application of this condition then
gives:
e.k = 0, (6.64)

which shows that e and k must be orthogonal. For a given ¢ and k there is
another unit vector that is orthogonal to both, so that there are two linearly
independent choices of e and these are distinguished by the subscript A = 1, 2;
the vectors €;,€ 2 and k are mutually orthogonal.
Clearly any pair of functions of the form 6.63 is also a solution of the
wave equation 6.59, so that the general solution is a sum over all possible
values for k and all polarizations A. However, in writing down this general
solution we insist that A(r, ¢) be real, since the fields B and E derived from it
must be real. This may be accomplished by taking:

AG) = > [aerMAnl®) + axOAR(l, (6.65)

where the asterisks indicate complex conjugation,

Art) = xa) exp (— iw 2) (6.66)

and
Axa(t) = Anta exp (iK.r). (6.67)
The general solution (Equation 6.60) can be written in this form by a suitable
choice of the coefficients and the wave vectors k; Equation 6.65 is just a
Fourier transform of Equation 6.60.
We will shortly need an orthonormalization condition for the vectors Ax(r),
but they cannot be normalized, since they are defined for all space. This prob-
lem may be circumvented by considering the special case of a large cubical
volume V of side Z centred on the origin. In calculations V can be made arbi-
trarily large and in the case of observable properties it will be seen that V dis-
The Classical Theory of Electromagnetic Fields 99

appears by cancellation. Inaddition,a periodic boundary condition is imposed by

requiring that A, ,(— sL, y, Z) = Aya(+ 5L, y, z) with similar conditions for
the other pairs of faces of the cube. The solutions of the second of Equations
6.62 are still given by Equation 6.67, but with the additional restriction that:

k = (2mn,,/L, 20nyy/L, 2nn,,/L), (6.68)

where y,, 2yy and ”,, are integers; these solutions are similar to the wave
functions for a particle in a box.
It may now be demonstrated that the A;,, are orthogonal to one another:

SARA NAT = (xn-€x’ VARA Ra’ S exp [i(k — k’).t]dz

= 65559’ lAnalV, (6.69)
where the periodic boundary conditions have been used to evaluate the volume
integral over the cube; use has also been made of the fact that the two possible
polarization vectors for a given k are orthogonal to one another. It will be seen
later that it is convenient to normalize the A, , to €!, so that the choice:

A= bal? (6.70)
is appropriate and the orthonormalization condition (Equation 6.69) becomes:

S Ak y-Ag'n'd7 = Sick’Ona’€o-- (6.71)

Although k can only take on discrete values (Equation 6.68), the side of
the cube may be made arbitrarily large and a sum over k may be replaced by
an integral:
% fik) > S fk)p(k)dk. (6.72)
The function p(k) is a number density and is defined so that p(k)dk is the
number of discrete values that k may adopt between k and k + dk. From Equa-
tion 6.68 it is apparent that:

p(k) = (L/2n)? = V/(27)?. (6.73)

Alternatively, it may be convenient to replace k by the polar coordinates k, 0,
¢. Since all directions of k are equally likely, we have:

o(k)dk = p(k)k?dkdQ = (Vk?/(2n)?)dkdQ, (6.74)

where dQ = sin @d@d@ is an element of solid angle. Finally, it is noted that
«(= kc) could be used as a variable instead of k, so that:

p(k)dk = p(w)dwdQ = (Veo"/(2mc)*)dwdQ. (6.75)

This result will not be used until Chapter 12.

100 Advanced Molecular Quantum Mechanics

6.7 The characteristic vibrations of an electromagnetic field

The Hamiltonian for an electromagnetic field is given by Equation 6.46:

H = f $€0(c?B? + E*)dr. (6.76)
If the discussion is again confined to a cubical volume V, this may be evaluated
using the solutions of the wave equation that have just been found, since from
Equations 6.53 and 6.65 to 6.67:

B= Vi A= RON i[dxa(Ok
, Ann — Tka(DK
y Akal (6.77)
and
E = —(0A/0t) = 2 1Ok [dxxaQAna —dka(Akal; (6.78)

it may easily be seen that a given wave vector and its contributions to B and E
are mutually orthogonal. From now on the dependence of the g,, on time
will be omitted for brevity.
The contribution of the electric field (Equation 6.78) to the energy (Equa-
tion 6.76) is:

f 7€0B "dr = — 3€0 ee Re Or [Dadar S Ana-An'a’dt

— qirdn'n' S Aka An’a'dT — Ceardnn S Aga Ann dt

+ gin gen S Aka An! d7]
2 hy PEM Murder + TATA + TrTier — TkErTKa]> (6.79)
where the orthonormalization condition (Equation 6.71) has been used; the
reason for normalizing the Ay, to €9' should now be apparent. (It will be
noticed that the order of gy, and qx has been preserved in Equation 6.79,
although this order has no significance in a classical theory. However, in the
quantum theory of Chapter 12 the order is important and for this reason it is
maintained in Equation 6.79 and subsequent equations.)
Using a modified form of the normalization condition (Equation 6.71) the
contribution of the magnetic field B (Equation 6.77) to the Hamiltonian is
found to be:
eae eae
569Gb AT = 5¢ eee (K n& a)(K ,€ cr) [GK x9-kr! + IEA GD’

+ Gadien’ + OEAd=Ka']- (6.80)

The quadruple vector product may be expanded using Equation 2.39:
The Classical Theory of Electromagnetic Fields 101

(Ky € xa)-(K pf ican’) = K7(Eqy- Ena’) — (K-€qy')(K-€4)

K°5yx" = (wile?)bar', (6.81)

where we have used the orthogonality of k and the two polarization vectors
associated with it. Thus:
1 1
S 3€0c°B7dr = 2 WET Ag-A + TEAK + MeaVta + agra). (6.82)

Addition of Equations 6.79 and 6.82 now gives the Hamiltonian for the
electromagnetic field:

= Ron WE(TEATKA + VerVEA): (6.83)

It is important to note that the total energy for the field is the sum of the
energies of the fields associated with each wave vector k and polarization A. In
addition, the Hamiltonian is expressed entirely in terms of the q,(¢), which
are the solutions of the first of the differential equations 6.62.
Using the same techniques the total momentum of the field G (Equation
6.48) may also be evaluated:

G= 2. Wiek(Guad-Kra + ITEAVKA + Verner + VKAW A): (6.84)

Since the summation is over all k, both positive and negative, the first and last
terms in the parentheses make no contribution to the total sum. (This depends
on the order of gy, and g_, as well as that of qi, and q*,, being unimpor-
tant; this is of course true classically and it will be seen to be true also in the
quantized theory of Chapter 12.) Thus:

ieee WeEK(GEAMKA + TkaTEa) (6.85)

and as for the energy the total momentum may be thought of as the sum of
contributions from the individual wave vectors and polarizations.
It is now convenient to define the new real functions of time:

Onn = Ara
t+ ka; Pax = —1Wx
(Gun — Vir): (6.86)
Reference to Equations 6.62 shows that the Q,, are just the real solutions of
the differential equation:
d’?Q/dt? + w’Q = 0, (6.87)

while from Equations 6.63 it is seen that the Py, are the time derivatives of the
Onn: b
Pyx = (dQxa/dt) = Qxx- (6.88)
102 Advanced Molecular Quantum Mechanics

The inverse of the transformation (Equations 6.86) is:

dun = (Quen + iP_a)/2x, (6.89)

so that in terms of the Q;,, and P, the field Hamiltonian (Equation 6.83) is:

H = 5D (Phat whQia)- (6.90)

The advantage of these new variables is that P;,, may be interpreted as the
momentum conjugate to Q,y, since Equations 6.87 and 6.88 are then consis-
tent with Hamilton’s equations of motion 3.34. In the first place the partial
derivative of the Hamiltonian (Equation 6.90) with respect to Py, is just Px,
which by Equations 3.34 must be equal to ene in accord with Equation 6.88:

(QHC/8P ur) = Pur = Ona: (6.91)

Secondly, Hamilton’s other equation requires that:

(8H/8Qxn) = RQ = — Pra (6.92)

substitution of Equation 6.91 in Equation 6.92 now gives:

Our + whOun = 0, (6.93)

which is just Equation 6.87 written in a different notation.
Again we note that the total Hamiltonian for the field may be written as a
sum of independent Hamiltonians, one for each wave vector and polarization:

se = PN Has Harn = 7(PEnx

+ weQ2,). (6.94)

Now #),, can be seen to be the Hamiltonian for a classical one-dimensional

harmonic oscillator, so that the field may be thought of as a collection of inde-
pendent vibrations or radiation oscillators. In addition, H,, is expressed in
terms of a coordinate Q,, and its conjugate momentum P,,); this is the start-
ing point for the quantization of the electromagnetic field, which is discussed
in Chapter 12.
Finally, we may note that the field momentum can also be expressed in
terms of the Q,, and P,, and that the total momentum (Equation 6.85) is
the sum of the contributions from the individual radiation osciallators:

G= 2% Gao, (6.95)
where
O 5 |= 7(k/w, (Pa + RO?)
(k/, Hy. (6.96)
The Classical Theory of Electromagnetic Fields 103

Bibliography

The classical theory of fields

Hameka: Section 6—1.
Landau and Lifschitz: Chapters 4 and 6.
Panofsky, W. K. H., and Phillips, M. (1962), Classical Electricity and Magnet-
ism, Addison-Wesley, Reading, Mass.
Sakurai: Chapter 1.

Continuous mechanical systems

Goldstein, H. (1950), Classical Mechanics, McGraw-Hill, New York: Chapter
Tle
CHAPTER SEVEN

Relativistic Wave Equations

We are now in a position to discuss the quantization of the classical relativistic

theory that has been developed in the preceding chapters. In a sense this chap-
ter is abortive, since it will become apparent that, although the wave equations
considered here may be appropriate to some particles, they do not describe
the electron; their major deficiency is that they cannot account for any of the
properties associated with the spin of the electron. However, this discussion
outlines the situation that faced Dirac and led him to propose the equation
that now bears his name; the Dirac equation is the subject of the next chapter.
In addition, the opportunity is taken to consider such topics as the gauge in-
variance of quantum mechanical equations.

7.1 Quantization of classical equations

The classical expression for the energy (or Hamiltonian) of a particle with mass
m and charge g moving under the influence of electromagnetic potentials A
and @ is (Equation 5.11):

E = c(m’c? + 1)? + a, (7.1)

where tris the mechanical momentum:

w = p—a@A. (7.2)

The usual prescription for the transition from a classical equation to a quan-
tum mechanical equation is to interpret the energy and the canonical momen-
tum as operators:
E = ih(a/dt); =p = —ifV, (7.3)
104
Relativistic Wave Equations 105

and to allow these to operate on a wave function w:

iM(Ow/at) = {c[m*c?+(p—gA)’}? + qa}y. (7.4)

This wave equation is unsatisfactory for two reasons. First, time and space
coordinates do not appear symmetrically, so that it is not clear whether it is
Lorentz invariant. Secondly, the presence of a square root term makes the
equation practically unusable, except when A vanishes or the particle is un-
charged; this problem is due to the fact that now p is an operator, p and A do
not commute and the meaning of the square root term is ambiguous. The re-
striction to a chargeless particle or to field-free situations is not acceptable, if
a wave equation for an electron is being sought.
Of course, if we are interested in a slow-moving particle, a non-relativistic
approximation may be obtained by expanding the square root term in Equa-
tion 7.1 as a power series in (1/mc):

E = me? + qo+ 17/2m — 14/8m3c? + O(me(n/mc)°). (7:5)

Neglect of terms of order mc?(m/mc)* and above and use of Equations 7.3 gives
for the quantum-mechanical version of this equation:

ih(aw/dt) = (mc? + qot n?7/2m)y. (7.6)

Except for the mc? term this is just the usual time-dependent Schrédinger
equation for a charged particle in an electromagnetic field.
The presence of mc? is merely due to the use of a different origin for the
energy scale. It may be removed formally by introducing a phase factor into
the wave function:
y—w' = Wexp(—imc’t/h). Ca)
The left-hand side of Equation 7.6 then becomes:

ih(aw'/at) = ih ma exp (— imc?t/h)]

exp (— ime’t/h)[ihap/at + me7y]. (7.8)

The exponential commutes with the operators on the right-hand side of Equa-
tion 7.6, which after rearrangement and premultiplication throughout by
exp (imc*t/h) becomes:
ih(aw/at) = (qotn’/2m)y. 9)

Thus the energy origin has been shifted by changing the phase factor of the
wave function; clearly this can have no effect on the physical properties calcu-
lated from the wave function.
106 Advanced Molecular Quantum Mechanics

Equation 7.9 is a time-dependent Schrodinger equation with the Hamil-

tonian operator:
KH = qot+n’/2m, (7.10)

and this may be expanded by substituting for the mechanical momentum t

(Equation 7.2):

H = qo+p?/2m—4q(p.A t+ A.p)/2m + q’A*/2m. (7.11)

The cross terms may be simplified by noting that:

p.A = A.p—ih(V.A). (7.12)

In obtaining this result it must be remembered that we are now dealing with
operators and that they must always be thought of as operating on a wave
function:
p.Ay = —iAV.AW = —ih[A(Vy)+(V.A)V]
[A.p —ih(V.A)] Vy, (7.13)
where the vector relation 2.64 has been used. If the Coulomb gauge (Equation
5.35) is being employed, the divergence of A vanishes and the Hamiltonian
(Equation 7.11) becomes:

H = qt p?/2m—(q/m)(A.p) + q7A?/2m. (7.14)

The first two terms in this Hamiltonian represent respectively the energy of
interaction of the charge with the electric field and the kinetic energy of the
particle. For a steady magnetic field B the vector potential may be written as
A= 5B at (Equations 5.37), so that the third term:

— (q/mA.p) = — (q/2m)B.r y p) (7.15)

represents the interaction of the magnetic field with the magnetic moment
(q/2m)(r , p) associated with the orbital angular momentum of the particle.
The final term represents the diamagnetic interaction; this arises because the
magnetic field induces some orbital angular momentum and the associated
magnetic moment then interacts with the magnetic field.
It is clear that there is nothing in the Hamiltonian (Equation 7.14) that can
be interpreted as either a magnetic moment or an angular momentum due to
the spin of the particle. If higher terms, such as — 7*/87m°c?, were retained in
the power series expansion (Equation 7.5) all the additional terms in the re-
sulting quantum mechanical Hamiltonian could be described as relativistic cor-
rections to the kinetic energy or the magnetic interactions in Equation 7.14.
It must be concluded that a wave equation based on Equation 7.5 does not
include anything attributable to spin.
Relativistic Wave Equations 107

7.2 Gauge invariance of quantum mechanical equations

In the last section it was assumed that the gauge of the electromagnetic
potentials can be chosen in quantum mechanical equations just as it can be in
classical equations. This assumption is now justified.
It is recalled that in a gauge transformation new potentials:

A’ = A-YVf; d = $+ (af/an), (7.16)

are introduced (Equations 5.31), where fis any scalar function of position and
time. This transformation does not alter the corresponding magnetic flux den-
sity and electric field strength. It will now be shown that, provided we also
introduce a phase factor into the wave function, a quantum mechanical equa-
tion is essentially unchanged, as it must be if it is to be gauge invariant. The
new wave function is chosen to be:

W' = exp (—igf/h); (7.17)

although the matrix elements.of individual operators may be different for y
and W’, the physical results calculated from these wave functions are the same.
The way in which ry behaves under the transformation is considered first:

my —(p—qA’)W’ = (p—qA + qVf)W exp (—iqf/h)

= exp (— iqf/h)(p —qVf—qA + qVf)y
= exp (—iqf/h) wy. (7.18)

Thustry is merely multiplied on the left by the phase factor in Equation 7.17,
and the same is true of 77W, m*y and so on. If (ihd/dt — q@)W is now exam-
ined, it will be seen that the effect of the transformation is the same:

(ihd/dt — gb) — (ihd/ot — qo — qofldt)y exp (—igf/h)

= exp (— iqf/h)(iha/ot + qof/ot — qo — goflot)y
= exp (— igf/h)(iho/ot — qg)y. (7.19)
The wave equation 7.6 can be rearranged so that, besides constants such as
mc?, the only operators that appear are m and (ihd/dt — qo). The combined
result of the gauge transformation (Equation 7.16) and the change of phase
(Equation 7.17) is to premultiply every term in this equation by exp (— iqf/h),
so that it is essentially unchanged. This conclusion is unaffected, if higher
terms in the expansion 7.5 are retained.
It is clear that any wave equation that, except for constants, can be written
entirely in terms of the operators mand (ihd/dt — q@) is also gauge invariant.
108 Advanced Molecular Quantum Mechanics

7.3. The Klein-Gordon equation

The wave equation 7.4 has the disadvantages that it is not obviously Lorentz
invariant, and that it is difficult to interpret and use. The first attempt to avoid
these difficulties was tp return to the classical Equation 7.1 and rewrite it as:

(E —q¢)? = c?(m’c? + 2”), (7.20)

before attempting to quantize it. Equations 7.20 and 7.1 are not exactly
equivalent, since the possibility that:
E = qo—c(mc?+ 1)? (721)
has been introduced. The leading term in an expansion of Equation 7.21 is
— mc? so that Equation 7.20 has some solutions with negative energy, that is
solutions which correspond to particles with negative mass.
If Equation 7.20 is quantized in the usual manner (Equations 7.3) the
corresponding wave equation is:

({hd/at — qo) = c?[mc? + (p—qA)’]¥; (7.22)

this is the Klein-Gordon equation. Since the square root term is no longer
present, it is unambiguous, and in addition the operators V and 0/d¢ both ap-
pear to second order so that the space and time coordinates occur symmetri-
cally and the Lorentz invariance of the equation is at least credible, if not
obvious. The invariance may be confirmed by noting that Equation 7.22 may
be rewritten as:
(mtc* Ferny, =. 0, (7.23)
where
fp, = —thojer, “q&a. (7.24)
is the component of a four-vector, since both 0/drg (Equation 4.51) and Ag
(Equation 5.2) are. Of course, the wave function will also be changed by a
Lorentz transformation, but it will be the same function of position and time
no matter what inertial frame is used.
Although the Klein-Gordon equation does not suffer from the disadvantages
of the wave equation 7.4, there are a number of objections to it which arise
from the way in which it is constructed. It has already been seen that the Klein-
Gordon equation has negative energy solutions; in fact, this is also true of the
Dirac equation, which is considered in the next chapter, but Dirac was able to
use this apparent deficiency to advantage. However, there are more serious ob-
jections to the Klein-Gordon equation, one being that for its solutions y*p
cannot be regarded as a probability density, since its integral over all space is
time dependent.
Relativistic Wave Equations 109

For a time-dependent Schrédinger equation:

HY = ih(dw/dt), (7.25)
the time and space variables may be separated by the substitution:

V(r, t) = x(1)O(0). (7.26)

This leads to two equations, the time-independent Schrodinger equation,
Hx = Lx, and an equation for 6(f):

in(d0/dt) = E6, (7.27)

the solution of which is:
6 = kexp (—iEt/h), (7.28)

where & is an arbitrary constant. The probability density y*y is thus propor-
tional to x*x and is time independent. Integration of y*w over all space shows
that a particle described by the wave Equation 7.25 has a constant probability
of being somewhere in space.
This is no longer true for a wave equation, such as the Klein-Gordon equa-
tion, in which the second derivative with respect to time appears. To demon-
strate this a simpler example is considered:

MW = =f (07W/ or): (7.29)

The variables may again be separated by the substitution of Equation 7.26, but
the time-dependent part 9(f) now satisfies the equation:

(d*6/dt?) = —a’0, (7.30)

where a (= \/E/f) is a constant. The general solution of this differential equa-
tion is:
6 = k,sinat +k, cos at, (7231)

so that y*w is in general time dependent and so is its integral over all space.
Consequently, the probability of a particle described by the Klein-Gordon
equation being somewhere in space varies with time.
In actuality many of the problems associated with the Klein-Gordon equa-
tion can be overcome, and it has been used to describe certain fundamental
particles, such as mesons, which can decay. In this connection it can also be
noted that the wave equation 6.59 for the electromagnetic field is just the
Klein-Gordon equation for a particle with zero mass and charge. Of course, if
a wave equation is to describe a decaying particle, some of the basic ideas of
quantum mechanics must be reformulated. For example, although the Klein-
Gordon equation is not consistent with the conservation of the number of
110 Advanced Molecular Quantum Mechanics

particles, it has been shown to be consistent with the conservation of electric

charge, which can be thought of as a more basic requirement; for an electron,
charge conservation and number conservation are equivalent.
Perhaps the most serious objection to the Klein-Gordon equation as a wave
equation for an electron is that it does not lead to anything that can be inter-
preted as spin. It must be concluded that, although the Klein-Gordon equation
may be appropriate to certain spinless particles, it is not a satisfactory equa-
tion for the electron and that a wave equation linear in the operator (0/01) is
necessary for the description of an electron.
Bibliography

Gauge invariance of quantum mechanical equations

Davies, D. W. (1967), The Theory of the Electric and Magnetic Properties of
Molecules, Wiley, New York: Section 2.3.
Hameka: pages 41-42.

The Klein-Gordon equation

Foldy: pages 14 and 40-46.

CHAPTER EIGHT

The Dirac Equation

The last chapter was devoted to showing that direct quantization of classical
equations does not lead to a wave equation for the electron. We will now dis-
cuss the Dirac equation for the electron. Although much of this chapter will
be concerned with its justification, it will be assumed from the outset that it
is indeed appropriate to the electron to the extent that we will refer to an elec-
tron with charge — e, where e is positive, rather than a particle with an arbit-
rary charge qg; in addition, m will now be taken to be the mass of the electron.
Let us briefly summarize the problem that faced Dirac. For a particle with
mass m and charge — e in the presence of electromagnetic potentials (A, ¢) the
classical relativistic expression for the energy is:

E= —eo+ c[m2c? + n?]?, (8.1)

where
w= pt+eA (8.2)

is the mechanical momentum. In the previous chapter this was interpreted as

a quantum mechanical equation by replacing the energy and the canonical
momentum by operators:

E = ina/at); p = —iAV, (8.3)

and allowing these to operate on a wave function y. However, such an inter-
pretation was seen to be unsatisfactory, since time and space coordinates do
not appear symmetrically and, except when A vanishes, the equation is un-
usable. These objections were removed at the expense of introducing solutions
with negative energy by starting with the classical relation:

(E + e¢)? = mc* +.c7n’; (8.4)

111
4 Advanced Molecular Quantum Mechanics

the substitutions 8.3 and the introduction of a wave function then gives the
Klein-Gordon equation. This too has a disadvantage in that the second deriva-
tive with respect to time appears with the consequence that the probability
that the particle is somewhere in space is time dependent. In addition, the
Klein-Gordon equation cannot account for the property of spin, so that, al-
though it might be appropriate for other particles, it does not apply to the
electron. It was this unsatisfactory situation that led Dirac to consider an
alternative equation.

8.1 The Dirac equation for a free electron

In the Klein-Gordon equation the time and space coordinates appear symmetri-
cally, but as second derivatives. Dirac argued that it is necessary for the time
coordinate to appear as a first derivative and, in order to preserve the relativ-
istic equivalence of space and time, it is necessary for the space coordinates to
appear as first derivatives as well. This would also be in contrast to the Schro-
dinger equation in which the time derivative is first order, but the space deriva-
tives are second order. To simplify the ensuing arguments we consider a free
electron, that is one in the absence of electromagnetic potentials. In addition,
the notation can be simplified by introducing the operator Po such that:

CPo = th(d/dt). (8.5)

(The subscript 0 is used rather than 4, because po is not the time component
of the four-vector py = — ih(0/0r,,), although they are related by p4= ipo).
The equation that Dirac proposed has the form:

[Po AxPx ~ AyPy ~ A), — Bmce] = 0, (8.6)

or in vector notation:
[Po—a.p —Bmc]y = 0, (8.6)
where the nature of @ and B needs to be considered more closely. In Equation
8.6 time and space coordinates do appear symmetrically, and one might expect
this equation to be invariant to Lorentz transformations, a necessary require-
ment of a relativistic equation; that the equation is indeed Lorentz invariant
will be confirmed later.
Since Equation 8.6 is to be an equation linear in space and time derivatives,
aand 6B must be independent of p and po. Also, we are considering the situation
where there are no electromagnetic fields so that all points in space-time are
equivalent and the operator [9 —a.p — Bmc] cannot involve x, y, z or f, since
this would introduce space-time inhomogeneity and anisotropy, although this
The Dirac Equation 113

operator can (and does) contain first derivatives with respect to these coordi-
nates; consequently @ and £ are also independent of x, y, z and t. To obtain
further information about « and 6 we return to the Klein-Gordon equation,
which for a free particle can be written in our current notation as:

[po — pz — Py — pz—m’e"]p = 0. (8.7)

Since this is directly connected with the classical expression for energy, the
solutions of the Dirac equation 8.6 are also expected to be solutions of the
Klein-Gordon equation 8.7. This is not the same as requiring that these two
equations have the same solutions; there will be solutions of the Klein-Gordon
equation, for which the probability of the existence of the particle will be time
dependent, and these cannot be solutions of the Dirac equation.
If we multiply the Dirac equation 8.6 on the left by the operator:

[Po = Ay Px ie Ay Py 7 a2Pz + Bmc] > (8.8)

we obtain a second-order equation in pp and the components of p, which can

be compared with the Klein-Gordon equation 8.7. In doing this the fact that
Po and the components of p each commute with 6 and the components of @
may be used, since we have seen that a and B must be independent of x, y, z
and ¢t. However, we must not assume that B, a,,, a, and @, commute with each
other, since their properties are yet to be determined. The result of multiply-
ing the Dirac equation by the operator 8.8 is thus:

[Po an a,Px o2 ay Py Suea,Dz ay Bmc] [Po AP ~ AyPy ~ AP, — Bmce] p

= [po — OZ Dps— 05 Py — 02D; — (OzAy + Oy, )PxPy

p= (a, a, xi aA, Ay PyPz ae (00, ie QA )P2Dx

— mc (a,.8 a Ba,.)Dx — mec (a8 aS Bay py

—mce(a,B + Ba, )pz — 6m? c7|y —s0: (8.9)

This is identical to the Klein-Gordon equation provided the following relations

between 6, a, @, and a, hold:

a =a, = 02 =f = 1;
(0,0 + GyQ,) = (Aya, +a,0,) = (4,0, +4,0,) = 0; (8.10)

(a8 + Ba) = (A,B + Bay) = (a,8 + Ba,) = 0.

If we let a = B (ap is not the coefficient of po and Q is not a component of a
four-vector), then these relations may be summarized as one relation:
114 Advanced Molecular Quantum Mechanics

[a,;, a]. = a0, tao; = 26 Gi = 0,x,y, 2), (8.11)

where §,; is the Kronecker delta. This equation shows that the four a; anti-
commute with one another and the square of each is unity.
Thus, provided Equation 8.11 is satisfied, multiplication of the Dirac equa-
tion by the operator 8.8 gives the Klein-Gordon equation and solutions of the
Dirac equation are also solutions of the Klein-Gordon equation. Although the
Dirac equation does not suffer from many of the objections to the Klein-
Gordon equation, there is still the possibility that solutions with negative
energy exist. We will return to this point later, when we consider positrons.

8.2. The Dirac operators a and 6

It is clear that B (=a) and the components of a cannot be numbers, since

they must satisfy the anticommutation relations in Equation 8.11; they can
be regarded as operators representing a new degree of freedom intrinsic to the
electron. It will be recalled that the spin angular momentum operators, 0,, Oy
and o,, of non-relativistic theory satisfy similar anticommutation relations
(Equation 2.22):
[o;, oJ, = 26;;. (8.12)

In addition, the properties of these operators can be represented by the three

two-by-two Pauli spin matrices so that it is reasonable to explore the possibility
that a,, @,, @, and 6 can also have a matrix representation. However, we will
see that we have to go to four-by-four matrices to achieve this.
The three two-by-two Pauli spin matrices:

( } F =< (/ 0
0, = Se Oyu = ~~ 6, = (8.13)
tL 6 eS i8) 0 -1

form a matrix representation of three quantities which anticommute with one

another and whose squares are unity; the square of each of the matrices (Equa-
tions 8.13) is unity in the sense that it is equal to the two-by-two unit matrix.
However, for a representation of the four a; we need four matrices, and any
attempt to find a fourth two-by-two matrix that anticommutes with o,., C.
and o, is doomed to failure. This can be seen merely by noting that any two-
by-two matrix can be expressed as a linear combination of o,, 0,, 0, and the
two-by-two unit matrix. Consequently there is no two-by-two matrix that anti-
commutes with all three components of o. (There is, of course, the trivial case
of the null matrix, but its square is not inity.) From this fact it can also be
The Dirac Equation 115

seen there are an infinite number of sets of three anticommuting matrices,

but that these are just orthogonal linear combinations of the components of o.
It might be thought that three-by-three matrices would be able to provide
us with four matrices with the required properties, but this can be disproved
by using some results of matrix algebra to show more generally that a matrix
representation of the a; can only be constructed from matrices of even order.
Let us consider a matrix representation A, B,.... This can be changed into an
equivalent representation X, Y,..., in which X is diagonal, by performing a
similarity transformation on each of A, B,...:

Xe" AO: ¥ =. 0-7 8G: een (8.14)

where Q is chosen to be the matrix that brings about diagonalization of A.
Many of the properties of the matrices are unaltered by similarity transform-
ations provided all matrices are subjected to the same transformation. If A and
B anticommute, then so do X and Y:

XY + YX = Q'AQQ 'BQ+Q'BQQ'AQ
= Q'(AB+ BA)Q = 0. (8.15)
Similarly, if A? equals the unit matrix, then so does X*. This fact, combined
with the fact that X has been chosen to be diagonal, means that the diagonal
elements of X must be either + 1 or— 1.
The next step in our proof is to show that the trace (the sum of the diag-
onal elements) of the matrix X vanishes. To do this we use the fact that for
two matrices R and S the trace of the product matrix RS is the same as the
trace of the product matrix SR; this can easily be proved by expanding
these products in terms of the elements of R and S (see Equation 2.108). Thus,
the product matrix XY” has the same trace as YXY, and also the same trace as
X, since Y? is required to be the unit matrix:

Tr (XX?) = Tr (XY) = Tr (X). (8.16)

However, since X and Y are to anticommute XY’ is equal to — YXY, so that:

THX ie TY XY): (8.17)

The only way in which Equations 8.16 and 8.17 can be reconciled is for the
trace of XY*, and hence of X, to be zero. But it has already been shown that
the diagonal elements ofX can only be + | or — 1, so that the number of diag-
onal elements with value + 1 must be the same as the number with value — i
and the order of the matrix must be even. Hence, only even-order matrices can
satisfy our initial assumption of anticommuting matrices whose squares are
116 Advanced Molecular Quantum Mechanics

the unit matrix. Consequently, we can move on to a consideration of four-by-

four matrices.
As was indicated earlier, there is a set of four-by-four matrices that forms a
representation of the @;. To arrive at this set (or one related to it by a similarity
transformation) in a rigorous fashion is somewhat involved, so that here a more
intuitive approach is adopted. Since the a; have properties similar to those of
the components of a, it is not unreasonable to use them as our starting point,
and we construct three four-by-four matrices by taking the direct product of
each of 0,, dy and a, (Equations 8.13) with the two-by-two unit matrix:

0). 1 Oned Or ein 1-0

linge Grete Onc) Jos LO ce BORkALO
Oro = 5 ON eae ‘ 2)
Gan ye aay Oo quinones;
On LOS eet oat) (Rae liege alls bes
(8.18)
(ee a. hey)
0. "—1 0 0
Gi, = >
ee ay he
0.0 ».0.5=1
it is common practice to use the same symbols for both the two-by-two and
the corresponding four-by-four matrices, since the context should indicate
which is intended. These four-by-four matrices satisfy the same relations (Equa-
tion 8.12) as the corresponding two-by-two matrices, that is they anticommute
with one another and their squares are the unit (four-by-four) matrix. The
possibility of constructing the a; by introducing just two new matrices p and 6
is now examined. The proposed relations are:

a, = po,; ay = POy; a, = po,; a, = Bp. (8.19)

It can easily be shown that for the a; (Equations 8.19) to satisfy the defining
relations (Equation 8.11) p and 6 must have the properties that their squares
are both equal to unity, that they anticommute with one another and that
they both commute with the components of o:

[0,014.05 (8.20)
[e,.0] = [Bo] = 0.
The Dirac Equation : 117

For example:

A~Ay FAVA, = PO,POy + poypo, = Gy0y + 0,0, = 0, (8.21)

or again:
A.Qo + Aa, = PO,B + Boo, = 0,(of8+Bp) = 0. (8.22)
When a matrix representation of the a; has been found, an equivalent repre-
sentation can be produced merely by performing the same similarity transform-
ation on each of the matrices in our original representation. However, the
representation can be fixed by stipulating that our representation is such that
6 is diagonal. In the consideration of general matrices it was seen that, for
the square of a diagonal matrix to equal unity, its diagonal elements can only
be + 1 or — 1 and that, for it to anticommute with other matrices, its trace
must be zero. Thus, 8 must have the same number of elements equal to + 1 as
equal to — 1. The fact that 6 commutes with o,, 0, and o, means that it can
only be:
RANOe FORO
OL ome
= (8.23)
Daly 40s ao
0 0 0-1
or of course minus this; we choose it to be as shown in Equation 8.23.
It remains to find the matrix p, which is to anticommute with 6 and to
commute with o,, 0, and o,, all of which are now known explicitly. From its
anticommutation property with B it can only have the form:

0 0 a b

0 0 Cc d
p= (8.24)
e if 0 0

g h 0 0

Commutation with o, demands that b, c, f and g are all zero, while commu-
tation with 0, (or o,) necessitates that d = a and h = e. Finally, for p’ to be
the unit matrix ge = 1 and making the choicea =e = 1:

ie AO Pew)
O wrOucSONM I
ne (8.25)
jie Sees 0)
Oe die 0 >-0
118 Advanced Molecular Quantum Mechanics

Substituting Equations 8.25, 8.23 and 8.18 into Equations 8.19 now gives us a
set of four four-by-four matrices representing the a;:

Om. OF Osakt 0 0 O -i
Oat Oe. sia traptigen 1a te
We leita 00g ee ee ee OC ne
NRO Ome 0 ae Oe 20
(8.26)
(Veep Reger Herow mig hes
0 0 O-1 gms hee Re:
oo . al aaOREO ge a eon Pow aie ae
Ot 0 0 Ne oy Mos 4
and as would be expected they are all Hermitian.
Although we do not prove it here, this is, to within a similarity transforma-
tion, the only four-by-four matrix representation of the a;. The particular
representation chosen here is called the standard representation. However, it
should be noted that as far as determining eigenvalues is concerned it does not
matter which representation is used, since, although the operator in the Dirac
equation:
[Po —a.p— Bmcly = 0 (8.27)

will have different forms in different representations, this is compensated by

a change in the wave function. If a similarity transformation is applied to the
matrices in the operator part of Equation 8.27:

i a; = Q'a;Q, (8.28)

where Q is independent of time and space coordinates, a new wave function

w’, is needed so that:
[Po—a’.p—Bimc]y' = 0. (8.29)
This is the same as Equation 8.27 multiplied on the left by Q”', if w’ is inter-
preted as:
y' =Q'y. (8.30)
Hence, use of a different representation merely transforms the wave function,
but certain representations will be more convenient than others, and for chemi-
cal applications the standard representation (Equations 8.26) is most appro-
priate, as will be seen shortly.
In the previous paragraph it is implied that the wave function w can be
The Dirac Equation 119

multiplied by a four-by-four matrix Q”!. Also the total Dirac operator can be
expressed as a four-by-four matrix, and this operates on W. This is only mean-
ingful if y is represented by a four-component column vector or spinor:

V1

pele (8.31)
se
Wa
and if Po is thought to be multiplied by a four-by-four unit matrix. Thus,
when expanded fully, the Dirac equation consists of four coupled equations
in the four components of yw:

(Po— me\W 1 — pzW3—(p, —ipy)W4 = 0

(Po— mc)¥2— (Px + ipy)W3t p24 = 0
(8.32)
—P2V1— (Px —ipy)W2 + Mo + meyy3 = 0
— (Px + ipy) bit pzW2t+ (ot mey4 = 0).
That the wave function y has four components needs some explanation. In
the spin theory due to Pauli the wave function of the electron is taken to have
two components corresponding to the two different spin orientations; thus
two-component wave functions would be expected in a theory that explained
electron spin. That twice as many components appear, is due to the fact that
solutions of the Dirac equation are also solutions of the Klein-Gordon equa-
tion, and negative energy solutions are possible. This can easily be seen from
Equations 8.32, if we consider the time-independent case, where Po is replaced
by E/c, and w is a function of space coordinates only. For a slowly moving
electron the magnitude of the momentum is negligible compared with mc, so
that Equations 8.32 have the approximate eigenvalues + mc? (twice) and — mc?
(twice). It is the small terms involving the components of p that couple these
so-called positive energy states and negative energy states making the theory a
relativistic one and adding relatively small energy corrections to + mc’. It is
now seen that the choice of the standard representation for the Dirac operators
provides the maximum separation of the positive and negative energy states.
Although it is the positive energy states that are of interest to chemists, the
negative energy states will be considered briefly later.
120 Advanced Molecular Quantum Mechanics

8.3. The introduction of an electromagnetic field

So far we have considered a free electron, that is in the absence of electromag-

netic potentials. These can be introduced in the usual manner by allowing the
replacements:
Po Po + (e/c)9; po n= pa eA, (8.33)
where allowance has been made for the definition (Equation 8.5) of Po and its
relation (Equation 8.3) to the energy. The resulting equation is:

[Po + (e/c)¢ —a.r— Bmcly = 0. (8.34)

From the considerations in Section 7.2 it is at once apparent that this equation
is gauge invariant, since it contains only the operators (p + eA) and (iA(0/dt)
+ e¢). A change in gauge merely multiplies the wave function by a phase fac-
tor, exp (— ief/h), where f is the scalar function specifying the gauge trans-
formation. In the special case of the time-independent problem Equation 8.34
reduces to:
[6mc? + ca.nr—edly = Ey (8.35)
and the operator on the left-hand side of this equation may be referred to as
the Dirac Hamiltonian.
The Dirac equation has now been developed, but it has yet to be shown that
it is appropriate to the electron. It has not been derived rigorously, nor can it
be; it came about because of an insistence on a linear equation in Po, D,,, Py and
pz, and a consideration of the consequences. Its justification is the same as
that for the Schrodinger equation — it works. Later in this chapter the Lorentz
invariance of the Dirac equation will be demonstrated and the nature of the
negative energy solutions will be considered. However, we will first show that
the equation is appropriate to the electron, in that it leads to the concept of
spin, since any further discussion would be pointless if this were not so.

8.4 Electron spin

Later in this chapter the relationship between the Dirac equation and the non-
relativistic formulation of quantum mechanics will be considered in detail.
Here, we will content ourselves with showing that, when the Dirac equation is
reduced to a non-relativistic form, two new properties arise naturally. These
properties are the intrinsic magnetic moment and the intrinsic angular momen-
tum, that are associated with spin.
The time-independent Dirac equation 8.35 can be written as:

Hy = By, (8.36)
The Dirac Equation Pel

where the Dirac Hamiltonian is given by:

H = Bmc* + ca.n— ed; (8.37)

if a matrix representation is used, then w is a four-component vector and H is
a four-by-four matrix. From Equation 8.37:

(H + e6)?/c? = (Bme + a.m)?

= mc? + (a.m), (8.38)
where the properties (Equation 8.11) of the Dirac matrices have been used; in
particular no cross terms arise on squaring (8mc + a.m), since a and 6 both
commute withrr, but anticommute with each other. To expand Equation 8.38
further, we note that «= po (Equations 8.19), where p is the four-by-four mat-
rix that has the properties (Equations 8.20) that it commutes with both # and
m , and has the unit matrix as its hae Hence:

(a.m)? = (0.1) = (o.n\(0.7). (8.39)

In Chapter 2 the relationship (Equation 2.43):

(o.B)(o.C) = (B.C) tio(B , C), (8.40)

was proved, where o commutes with B and C and the components of o are the
two-by-two Pauli spin matrices. Although the o used in Equation 8.39 are four-
by-four matrices, they are constructed (Equations 8.18) from the Pauli matrices
and satisfy similar commutation and anticommutation properties. Thus, since
o and mcommute, Equation 8.40 can be used to expand Equation 8.39 pro-
vided it is remembered that four-by-four matrices are now involved:

(o.m)* = 17+ i0.( 1,7). (8.41)

It is tempting to say that the second term in this equation is zero, since it in-
volves the vector product of rm with itself, but this is not true. In considering
(mtr) the explicit form ofm (Equations 8.33) must be used:

mw, = (pt eA),

(pt eA)

ll PrpteprAtA np) t+erA yA. (8.42)

Although the first and last terms in this equation do vanish, the middle term
does not, since p and A do not commute; this term may be simplified further,
but in doing so it must be remembered that it is an operator and must always
be thought of as operating on a wave function, even though the wave function
is not included explicitly. Thus:
12 Advanced Molecular Quantum Mechanics

a > a II e[p,pAtA
yp]

I| —ihe(V,A) = — iheB, (8.43)

where B is the magnetic field associated with the potential A (Equation 5.20).
In going from the first to the second line the vector relation 2.65 has been
used to expand (V, Ay):

(V, AY) = W(V ,)A)—(A AVY. (8.44)

Combining Equations 8.38 to 8.43 gives:

(H + e)?/c? = mc? + 1 + ehoB. (8.45)

Since we are interested in comparing the Dirac equation with non-relativis-
tic theory, we wish to consider Equation 8.45 in the non-relativistic limit, that
is when it is applied to a slowly moving electron. The Hamiltonian for a posi-
tive energy state can then be written as:

i — mc +o. (8.46)
where J’ is small compared with mc’. In expanding the left-hand side of Equa-
tion 8.45 it can then be assumed that H’*/c? is negligible as are other terms
involving c:
(H + e¢)?/c? ~ mc? + 2mK' + 2me?. (8.47)
Combining Equations 8.45 and 8.47 gives finally:

KH’ ~ —ept+n?/2m + (eh/2m)o.B; (8.48)

this confirms that H’ is negligible compared with mc’. This Hamiltonian is the
same as the non-relativistic Hamiltonian for an electron except for the term
(eh/2m)o.B, which may be interpreted as an additional potential energy due
to an interaction with the external magnetic field. That is the particle possesses
a magnetic moment:
—(eh/2m)o = — 2ups, (8.49)
where Ug (= eh/2m) is the Bohr magneton and s = @/2. This is just what is as-
sumed in introducing spin into the non-relativistic Hamiltonian (see Chapter 1).
Of course, a matrix representation of the Hamiltonian (Equation 8.48) in-
volves four-by-four matrices, but consideration of the specific forms of the
components of o (Equations 8.18) shows that, when it operates on a four-
component wave function, the Hamiltonian factorizes into two identical pairs
of coupled equations. Hence, Equation 8.48 with a four-by-four matrix repre-
The Dirac Equation 23

sentation of o conveys no more information than the same Hamiltonian with a

representation involving two-by-two Pauli matrices. This is in accord with the
two-component formalism of non-relativistic spin theory.
To obtain the g value appropriate to a particle which satisfies the Dirac
equation it is necessary to obtain the intrinsic angular momentum associated
with the intrinsic magnetic moment, since the g value is related to the ratio of
the magnitude of these quantities. The intrinsic magnetic moment gives rise to
potential energy, but the intrinsic angular momentum does not and its presence
must be demonstrated in a different fashion. To do this we consider a free
electron, that is in the absence of electromagnetic fields. The Dirac Hamiltonian
now has the simpler form:

H = Bmc? + c(a.p). (8.50)

In the non-relativistic quantum theory of a free particle the Hamiltonian,
H = p?/2m, and the orbital angular momentum, Al=r AP, commute with one
another and /lis a constant of motion. To prove this we consider the commu-
tation of the component Ail; with p? and use the techniques of Chapter 2:

[Al;,p°] = [€ijerjPr. PiPl

Il
2ihe; j,51j;P1Pr = 0. (8.51)
However, it willbe seen that Al does not commute with the Dirac Hamiltonian
(Equation 8.50) since:

[Al;,H] = he[l;(a.p) —(a.p)i;]

= hca.|{];, p] (8.52)

and J; does not commute with p. In fact:

(i,j) = tijnPrs (8.53)

so that:

[Al;, IH] IhCE; jn; Pr

ihcp(o,Pp)i, (8.54)

where « has been replaced by poe (Equations 8.19).

The orbital angular momentum Ail is no longer a constant of motion. This
implies that Al is not the total angular momentum associated with a particle
satisfying the Dirac equation. The appearance of o in Equation 8.54 suggests
that a consideration of the commutator of o with H might be pertinent. Re-
membering that 8 commutes with « (Equations 8.20):
124 Advanced Molecular Quantum Mechanics

[o;, #] = c[o;(a.p) — @.p)oi]

c[o;,a].p = cp[o;, o].p, (8.55)

where again Equations 8.19 and the properties of p (Equations 8.20) have
been used. Now the commutation properties of the components of o are
(Equation 2.41):
[o;,0;] = 2i€; jn0p; (8.56)

this relationship holds whether a four-by-four or a two-by-two matrix repre-

sentation is used for the components of a. Substitution in Equation 8.55 gives:

[o;, H] ll CP21€; jp OpP;

= —2icp(opPii (8.57)
showing that o does not commute with the Dirac Hamiltonian either. However,
comparison of Equations 8.54 and 8.57 shows that (Al + sh o) does commute
with #:
[Al, + $ho;, H] = 0, (8.58)
and is thus anew constant of motion. If we regard this as the total angular mo-
mentum, then in addition to the orbital angular momentum Al there is an in-
trinsic angular momentum sho and by identifying o with 2s this intrinsic
angular momentum of As is just what is assumed in non-relativistic theory (see
Chapter 1).
The Dirac equation thus leads to an intrinsic magnetic moment of — 2ugs
and an intrinsic angular momentum of hs. The ratio of these gives a g factor of
2. These results agree with the assumed electron properties that are introduced
phenomonologically into the non-relativistic theory of the electron. It would
appear that the Dirac equation is indeed an appropriate equation for the elec-
tron. However, we still have to verify the Lorentz invariance of the equation
and examine the negative energy solutions more closely before its suitability
is fully confirmed.
It is often said that electron spin is a consequence of special relativity, since
it was first explained by the relativistic theory of Dirac. However, it is only
fair to say that there is another point of view. The non-relativistic Hamiltonian
(Equation 7.10) for a particle contains the operator 17/2m. Replacement of
this by (o.1)’/2m, where the components of o are the Pauli spin matrices, also
leads to an intrinsic magnetic moment of the right magnitude, as may be seen
from Equations 8.39 to 8.45. The same method may be used to develop a rela-
tivistic theory, the result being the Dirac equation; this approach is described
in, for example, the book by Sakurai (see bibliography).
The Dirac Equation M25

Finally, it should be pointed out that the present section has itself raised a
problem in that | and s, which commute with the non-relativistic Hamiltonian,
do not commute with the Dirac Hamiltonian; the reasons for this will be dis-
cussed in Section 8.10.

8.5 Lorentz invariance of the Dirac equation

Although the Dirac equation was constructed so that time and space coordi-
nates appeared symmetrically, it is not at all obvious from Equation 8.34 that
itisin fact Lorentz invariant. It need hardly be said that for the Dirac equation
to be an acceptable relativistic equation it must be Lorentz invariant.
In most advanced texts the invariance with respect to a general Lorentz
transformation is demonstrated. Here we will content ourselves with the
specific transformation considered in Section 4.3. That is, we consider two
inertial frames K and K’, for which the axes x and x’ coincide and the axes
y and z are parallel to y’ and z’ respectively; the velocity of the K’ frame is v
relative to the K frame. A general Lorentz transformation can be reduced to
this specific one merely be redefining the origins and the orientation of the
axes within the two frames.
It will be recalled that the coordinates, x, y, z and t, in the K frame are re-
lated to x’, y’, z’ and t', the coordinates in the K’ frame, by Equations 4.18:

Puy TE) = 40 2 eV WC al oo)

where y = (1 —v7/c?)"2. For the present purposes it is convenient to rewrite

Equations 8.59 using Equations 4.9 and 4.11:

eos COSC
ier si 0. eas
(8.60)
7A a A t = t' cos @ —i(x'/c) sin @,

where (Equation 4.14):

tan @ = iv/c; (8.61)

6 is the parameter used in Chapter 4 and can be seen to be independent of the

space and time coordinates. In Chapter 5 it was noted that the electromagnetic
potentials, A,,A,,A, and ¢/c?, transform in a similar fashion:

A. =
II A, cos) —1(6 Jc) sin @; A, = Aj;
(8.62)
Am ¢ = ¢' cos
0 —icA, sin 0.

The operators 0/074 have also been shown to transform as the components of
a four-vector (Equation 4.51), so that, recalling the definition of po (Equation
126 Advanced Molecular Quantum Mechanics

8.5), the operators Px, Py, Pz and Po transform as:

II D.. cos 0 — ipg sin 8; Pys= Dy
i (8.63)
P2 = Diy po ="pocds
8 —p, sing.
By substituting Equations 8.62 and 8.63 into the Dirac Equation 8.34, we
obtain, after some rearrangement:

[(cos 0 + ia, sin 0)(p5 + (e/c)d’) — @,,(cos 0 + ia, sin 0),

—aym,
yy
—a,7, —Bmcly = 0, (8.64)
where w is still the wave function in the unprimed frame of reference. To show
that the Dirac equation is Lorentz invariant it is necessary to demonstrate that
it has the same form in both the primed and the unprimed frames. That is, we
must show that Equation 8.64 is equivalent to:

[po + (e/c)¢' —a.m' — Bmcly' = 0, (8.65)

where w’ is the wave function appropriate to the primed frame of reference.
This can be achieved in the following way. The first thing to note is that ex-
pressions such as sine and cosine can always be interpreted as power series in
their arguments and thus there is no objection to their arguments involving
matrices. Since sine and cosine are, respectively, odd and even functions of
theri arguments and the square of a, is the unit matrix we can write:

cos @ + ia, sin? = cos (6a,)+isin (0a,) = exp (i0a,). (8.66)

No problems arise about the order of @ and a, in these expressions, since @ is

a constant and commutes with a,, and the interpretation of Equation 8.66 is
unambiguous. Also, a term of the type exp (i0a,.) commutes with a, and the
operators (p09+ (e/c)¢’), 7, Ty and 7, but it does not commute with ay, @, or
6. By expanding the exponential as a power series and using the anticommuta-
tion properties (Equation 8.11) of a, with a,, a, and 8, it can be seen that:

exp (i0a,,)a, = ay exp (— i0a,.); (8.67)

similar expressions hold for a, and B. Thus, by multiplying Equation 8.64 on
the left by exp (— 16a, /2) and altering the order of the terms using relations
of the type in Equation 8.67, the transformed Dirac equation becomes:

[Po + (e/c)$' — a.m’ — Bmc] exp (i0a,,/2)W = 0, (8.68)

which is identical to Equation 8.65 provided that w’ is interpreted as
exp (i0a,/2). Hence, the Dirac equation in the K frame transforms into a
The Dirac Equation 127
. . . .
similar equation in the K frame, the wave function transforming as:
rt . :

yy = exp (i0a,./2)W. (8.69)

Although the Dirac equation itself is invariant to the transformation, it is

still necessary to show that the physical interpretation ofits solutions is also
independent of the frame of reference used. For example *y is the proba-
bility density in theK frame, so that W’*W’ should be the probability density in
the K’ frame. (The expression "Wy is the scalar product of , the four-compo-
nent column vector (Equation 8.31), and its Hermitian conjugate y*. The
Hermitian conjugate of a matrix is obtained by taking its complex conjugate
followed by transposition, so that W* is the four-component row vector (V7,
V3, W3, W4); in general the Hermitian conjugate of a matrix with elements R;;
is the matrix with elements R};. For future use we note that Hermitian conju-
gation of a product matrix results in a change of order of the factors, that is
(AB) = B*A*, as may be confirmed by expanding the matrices in terms of their
elements.) The two quantities, Y*Wy and y'ty’, are not expected to be the
same in the two frames, since yy is the probability of finding the electron at
a point in space in the K frame and the Lorentz transformation mixes the
space and time coordinates. Thus, the specific Lorentz transformation under
discussion would change a volume element dxdydz in the K frame to a mixture
of dx'dy’dz’ and dr’dy’dz’ in the K’ frame. That is, the probability density in
the unprimed frame transforms into a mixture of the probability density and
the x’ component of the probability current density in the primed frame; the
probability current density is just the probability of the electron crossing unit
area in unit time. Thus, we have to show that W*W transforms like the time
coordinate t, when subjected to a Lorentz transformation. Under the trans-
formation:
vey II [exp (0a,,/2)W]* exp (10a, /2)y

W* exp ((0a,,/2) exp (10a, /2)y, (8.70)

since a, is real (Equations 8.26) and Equation 8.61 shows that @ is pure
imaginary. Hence:
vty — W* exp (i0a,)Y = YWcosé +ip*a,yp sin 8, (8.71)

and W*w does indeed transform like the coordinate t, while comparison with
Equations 8.60 shows that it is W*ca, that transforms like the space coordi-
nate x; it willbeseen in Section 8.10 that cais the electron’s velocity operator,
so that w*cay is indeed the probability current density.
Finally, it must be demonstrated that the electron’s charge is conserved,
that is the change in the charge density in an infinitesimal volume element
must be compensated by a flow of charge across the faces of the volume
128 Advanced Molecular Quantum Mechanics

element. This conservation condition may be expressed as (Equation 2.55):

(dp/dt) + V.j = 0. (8.72)

In the present connection the charge density p and the current density jboth
differ by a factor —e from the probability density y*y and the probability
current density *caw, respectively, so that Equation 8.72 may be rewritten as:

aW*W)/at
+ V.Wy*cay) = 0. (8.73)
That the relationship is obeyed may be demonstrated by multiplying the Dirac
equation 8.34 on the left by y*:

W*[Gh/c)(OW
/dt) + (e/c)dy] — Ya. [—ihVY + eAY] —Bmep"y = 0.(8.74)
The Hermitian conjugate of this equation is:

[— ih/c(*/at) + W*(elo)g]y — [iA(VY*) + VeA].ab — Bmey"y = 0,

(8.75)

where use has been made of the fact that the components of « are Hermitian
so that (Wa) =aw. By subtracting Equation 8.75 from Equation 8.74 and
dividing by (ih/c):

W*(ow/dt) + (OW*/aOW + Y*ca(VY)+(VY").cay = 0, (8.76)

which is merely an expanded form of Equation 8.73. Thus, the Dirac equation
is consistent with the conservation of charge.

8.6 The negative energy solutions — positrons

We have already seen that the Dirac equation for a free electron has four solu-
tions, which is twice as many as is needed to explain spin. This multiplicity of
solutions arose because half the solutions have negative energies. In fact, this
happens in any relativistic theory, even classical ones, since the energy always
involves a square root (see for example Equation 8.1), which can have both
positive and negative values. Classically the positive square root is taken, the
presence of negative solutions causing no embarrassment. This is because classi-
cally the energy must vary continuously, and energies between + mc? and
— mc’ are not permitted, so that, if the energy is positive at one time it cannot
become negative at a later time. However, quantum mechanically discontinuous
transitions can occur so that the negative energy solutions cannot be ignored.
The solutions of the Dirac equation are represented by a wave function
which is a four-component vector or spinor:
The Dirac Equation 129

y= (8.77)

ieee.
(Os AO
Ota, wee Oas0
oS (8.78)
O08 10
0 0 OSI

in the matrix representation that we are using, Y,; and W2 may be thought of
as positive energy components and 3 and wW, as negative energy components.
For solutions with positive energy the main components will be Y, and W2, but
small amounts of Y3 and 4 will be mixed in by the terms a.m which couple
positive and negative energy components. In this section the relationship be-
tween the positive energy solutions and the negative energy solutions will be
examined, and it will be shown that if the positive energy solutions correspond
to a particle with electric charge — e, then the negative energy solutions may
be thought of as being for a particle with the same mass, but with charge + e.
The Dirac equation for a particle with charge — e:

[Po + (e/c)d —a.(p + eA)— Bmcly = 0 (8.79)

has as its complex conjugate:

[— Po + (e/c)o —a*.(— p + eA) — Bc]p* = 0; (8.80)

although 8, a, and a, are real, a, is imaginary (Equations 8.26) so that the
complex conjugate of a must be written as a™. A new real matrix y (not to be
confused with the number y in Equations 8.59) is now introduced:

Yo 1b a. (8.81)
Using the anticommutation relations (Equation 8.11) of B and the compo-
nents of a, together with the fact that af = —a,, the following properties of
y may be demonstrated:

NOS OY eye — ay. (8.82)

Multiplication of Equation 8.80 on the left by — y followed by the use of
130 Advanced Molecular Quantum Mechanics

these relations leads to:

[Po
— (e/c)d —«.(p —eA) —Brnc]yp* = 0. (8.83)
Comparison of this equation with Equation 8.79 shows that, if W is a solution
of the Dirac equation, then yw* is a solution of the same equation, except
that the sign of the charge has been reversed. That is, if y is a solution of the
Dirac equation for a particle with charge — e subject to electromagnetic poten-
tials, then yw* is a solution of the Dirac equation for a particle of charge + e
subject to the same electromagnetic potentials. For this reason ¥ is referred to
as the charge conjugation operator.
It can easily be shown that if w is a positive energy solution then yw™ is
a negative energy solution, since from Equations 8.26, 8.77 and 8.81:

O20 <0. uve wa

Oc Ott = pOe als —y*
yu = ipa = ER AN = de pel (8.84)

stat Gehry ini *

W being a positive energy solution, Y; and W2 are the main components, so
that for y* it is the negative energy components that predominate and yy* is
a negative energy solution.
This demonstrates that the negative energy solutions of the Dirac equation
may be thought of as corresponding to anew particle having the same mass as
the electron, but opposite charge. These particles are given the name positrons
and were first suggested by Dirac in 1930. Their discovery in 1933 by Ander-
son can be regarded as a triumph of the Dirac theory. Since then a number of
other so-called antiparticles have been recognised.
However, there are still a number of problems associated with the concept
of positrons and the situation cannot be as simple as it has been described
above, since the theory so far implies that a positron has a negative kinetic
energy. Dirac avoided this difficulty by supposing that nearly all the negative
energy states are occupied with one electron in each state, in accordance with
the Pauli exclusion principle. An unoccupied negative energy state then appears
as having positive energy, since to remove it an electron with negative energy
must be introduced. Dirac suggested that these unoccupied negative energy
states or holes are, in fact, positrons. This picture suggests that, if an electron
makes a transition from a positive energy state to a negative energy state, as-
suming that there is one unoccupied, then this would be interpreted as the
simultaneous disappearance of both an electron and a positron with the release
The Dirac Equation ed

of an enormous amount of energy as electromagnetic radiation. The reverse

process would involve the creation of an electron and a positron out of electro-
magnetic radiation. It can be seen that this theory is symmetrical between
electrons and positrons, and that a theory using the positron as the basic par-
ticle could be developed. These ideas lead to the concept of antimatter uni-
verses.
Although this assumption of occupied negative energy states solves some
problems, it introduces further difficulties, since it implies that there is an in-
finitely dense distribution of electrons everywhere, and that for a perfect vac-
uum all the negative energy states are filled while all the positive energy states
are unoccupied. For Maxwell’s equations to hold it is necessary to assume that
this infinitely dense distribution of electrons does not contribute to electro-
magnetic fields, and that Maxwell’s equations only apply to departures from
the vacuum state.
It can thus be seen that this theory is by no means satisfactory, but all the
difficulties can be avoided by using quantum electrodynamics. However, chem-
istry is concerned with positive energy states and this topic will be pursued no
further.

8.7. The non-relativistic approximation of the Dirac equation

The Dirac equation is an appropriate relativistic quantum mechanical equation

for the electron. However, it suffers from the disadvantage of being a four-
component equation; that is, it involves four-by-four matrices and the wave
function is a four-component vector. In this it differs from non-relativistic
equations, whose wave functions have two components corresponding to the
two possible orientations of the electron’s spin. The Dirac equation has, in
addition, two negative energy components, which are coupled to the positive
energy components. Since chemistry is concerned only with the positive energy
solutions it would be advantageous to decouple the positive and negative energy
components to give a two-component equation for the positive energy solu-
tions which would be similar to the non-relativistic equations and could be
used in the same way; by decoupling the positive and negative energy compo-
nents the Dirac equation would in effect be reduced to a non-relativistic form.
Two methods of performing this decoupling will be examined. In the next
section the method of small components is briefly considered, since this is the
method normally used in the few places that the Dirac equation is discussed in
the chemical literature, and a number of texts do not appreciate an important
point. The Foldy-Wouthuysen approach is described in detail in Section 8.9.
In principle both the methods may be used to decouple the positive and
negative energy solutions completely, but in practice this is only possible in
132 Advanced Molecular Quantum Mechanics

special cases (see Section 8.10). In both methods the Hamiltonian is obtained
as a power series, which converges for electrons moving with velocities much
less than the speed of light. Thus there are a number of problems shared by
the two methods, the choice of expansion parameter for the power series, the
estimation of the size of the various terms in the series and the decision on
how far to take the expansion. The remainder of this section will be devoted
to these questions.
A number of quantities have been used as the power series expansion par-
ameter, c', (u/c) and a, where wu is the speed of the electron and a is the
fine structure constant (not to be confused with the Dirac operator @ or its
components). The quantity c”' is frequently used, but it is not really suitable,
since it is not dimensionless and consequently its value depends on the system
of units employed. Both (u/c) and @ are dimensionless and we will shortly see
that they are in a sense equivalent. However, we will make the more professional
choice of the fine structure constant a, which is defined by:

a = e*ugc/2h = e?/2hegc = 7:29735 (+ 0-00001) X 107°; (8.85)

it is a fundamental constant of importance in atomic spectroscopy and, since

it is dimensionless, its value is independent of the units used.
Now the largest term in the Dirac Hamiltonian (Equation 8.37) is mc?, so
that it is appropriate to estimate the magnitude of other terms relative to this.
It will be seen that the order of magnitude of each of the other terms in the
Hamiltonian, e?, ca.p and cea.A, can be expressed as mc’a”. Since chemists
are concerned with atoms and molecules, it is appropriate to consider their
magnitude in an atomic or molecular environment and for this purpose we
choose the simplest possible situation for an electron, the hydrogen atom.
In the first Bohr orbit the electron’s speed is u = e?/2€9h = ca, and it is
now seen that a and (u/c) are comparable expansion parameters;in addition
the radius of the first Bohr orbit is ag = 4m€9h?/me?. Thus, classically:

ca.p~cmu = mc’a, (8.86)

while from Equation 5.61:

ed ~ e7/4m€ga9 = me7a’. (8.87)

The magnitude of the electric field encountered by an electron in the first
Bohr orbit is, from Equation 5.60, e/4m€9a3~ 5 X 10!!Vm"!," which is con-
siderably larger than electric fields found in the laboratory; consequently, ex-
ternal electric fields do not affect this estimate that e¢ is of order mc7a?.
To find the order of magnitude of the term cea.A, we use the magnitude
eu/4m€ Cd (Equations 5.72) of the magnetic potential at the proton due to
The Dirac Equation 133

the motion of an electron in the first Bohr orbit. Hence:

cea.A ~ e7u/4m€9cag = me?a?. (8.88)

The contribution to cea.A from the electron spin magnetic moment is of the
same magnitude, while nuclear contributions are smaller than this by a factor
of the order of (7/M), where M is the mass of the proton. In addition, the
internal magnetic field in the hydrogen atom is of the order of eu/4m€9c7a2 ~
10T (10°G), whichis an order of magnitude larger than external magnetic fields
normally realizable in the laboratory. It is concluded that cea.A is of the order
of mc?a?.
The two parts of ca.w=ca.(p + eA) are thus of different orders of magni-
tude and could be treated separately, but it is advantageous to keep them to-
gether so that any resulting Hamiltonian is gauge invariant (Section 7.2). In
any application of the Hamiltonian negligible terms in A may be omitted after
the gauge has been chosen and the magnitude of these terms has been esti-
mated.
It will be seen that the magnitude of any term that arises in the expansion
of the Dirac Hamiltonian in a non-relativistic form can be estimated from these
results. It has been noted that in principle the positive and negative energy
solutions can be completely decoupled, but in practice the manipulations in-
volved become tedious in going beyond an approximation correct to order
mc’a*. However, this is not a serious disadvantage, since higher order correc-
tions are in general not at present observable and, in addition, at this order
radiative corrections become important and a quantum electrodynamic treat-
ment becomes essential. The positive and negative energy states can be com-
pletely separated in some specific situations; the free electron is one of these
special cases and is treated in detail in Section 8.10, since it gives an insight
into the connection between the Dirac equation and its non-relativistic approxi-
mation.

8.8 The method of small components

In the method of small components the starting point is the time-dependent

Dirac equation 8.34. Since it is an electron with positive energy that is of
interest, we remove the rest mass energy for positive energy states (+ mc’) by
introducing an appropriate phase factor into the wave function:

y—w’ = exp(— ime?t/h)w. (8.89)

Substituting in Equation 8.34 the Dirac equation then becomes:

[Po + (e/c)d — (a.m) — (B— I)me]y = 0. (8.90)

134 Advanced Molecular Quantum Mechanics

The wave function w is still a four-component vector (Equation 8.31), but it

can be rewritten as:

y = a (8.91)
p_

where W, and y_ are two-component vectors:

1 W3
Y= [ : y= | ; (8.92)
WY Wa

W, has as its components the positive energy components, ; and 2, while

W_ has W3 and Wa, the negative energy components. The solutions of interest
are those in which the positive energy components W, predominate, and con-
sequently the two components of , are called the large components while
those of w_ are the small components; it is the latter that are to be eliminated.
Using the substitution (Equation 8.91) and the explicit form of the Dirac
matrices (Equations 8.26), Equation 8.90 can be rewritten in terms of the
two-by-two Pauli spin matrices (Equations 8.13):

[Po + (e/c)¢]W.—(o.my_ = 0
(8.93)
[Do + (e/c)¢]W_-—(o-m W, = 0).
+ 2mew_
These equations are coupled and each involves two-by-two matrices and two-
component wave functions.
The second of these coupled equations can be used to express the small
components W_ in terms of the large components W,:

y- = [2me + po + (e/c)¢] “(o-m)¥.. (8.94)

The presence of 2mc in the denominator justifies the description of w_ as the
small components. Substitution of Equation 8.94 into the first of the Equa-
tions 8.93 gives an equation involving only ,:

[Po + (e/c)— (1/2me)(o.m)K(om)]y, = 0, (8.95)

where the Hermitian operator K is given by:

K = [1 + (pot (e/c)¢)/2me]"!. (8.96)

Identifying cpo with ih(d/dt) (Equation 8.5), Equation 8.95 can be written as:

Hy, = ih(dw,/dt) (8.97)

with the Hamiltonian given by:

H = —ep + (1/2m)(o.m)K(o.m). (8.98)

The Dirac Equation 135

For the case of a slowly moving electron K can be approximated by unity

and the Hamiltonian becomes:

H = —eg+(1/2m)n? + (eh/2m)(o.B), (8.99)

where we have employed manipulations similar to those used in obtaining
Equation 8.45 from Equation 8.38. Again we note that the Dirac equation
leads to a term in the Hamiltonian that demonstrates that the electron has an
intrinsic magnetic moment. The non-relativistic Hamiltonian (Equation 8.99)
has already been obtained in Section 8.4, but the present method can be used
to obtain further relativistic correction terms by expanding K as a power series.
However, the manipulations involved may be facilitated by two results, which
will first be derived.
For any operator G, we may write:

(G,K] = K[K",G]K = K[po + (ele)¢,G]K/2mce, (8.100)

where Equation 8.96 has been substituted for K '. This relationship may be
used to move the operator K to the right in any operator expression, and this
is done at the expense of introducing the additional but smaller term given in
Equation 8.100; in practice the new terms are two orders of magnitude smaller
in aw and the convergence is quite dramatic, as will be seen.
When K has been moved to the right-hand end of an operator expression,
some sort of substitution is needed for it. This may be found by noting that
in this problem the Hamiltonian (Equation 8.98) only operates on W, so that
an approximation for Kw, is needed. From Equation 8.96:

Po + (e/c)¢ = 2mc(K™*— 1), (8.101)

and substitution of this into Equation 8.95 followed by premultiplication
throughout by K gives, after rearrangement:

Kw, = [1 —K(oe.m)K(o.m)/4m’c’|W,. (8.102)

This may be expanded by using Equation 8.100 and Equation 8.102 itself,
together with the identity:

[Po + (e/c)¢, 6.1] = — (ihe/c)(o.E), (8.103)

which is obtained with the help of Equation 5.21. To the order of accuracy
that we require the result is:

Ky, = [1 —(em)*/4m’c?
+ O(a*)]y,. (8.104)
Equations 8.100, 8.103 and 8.104 may now be used to expand the Hamil-
136 Advanced Molecular Quantum Mechanics

tonian (Equation 8.98), which becomes after some manipulation:

H = —ed + (o-m)*/2m — (o.m)*/8m°c?

+ (ihe/4m?c’)(o.m)(0.E) + O(mc’a*); (8.105)
the order of magnitude of the terms has been estimated using the information
given in the previous section. This Hamiltonian cannot be correct, since the
last term is not Hermitian. However, this defect may be remedied by noting
that W,, the wave function associated with Equation 8.105, is not normalized;
for the Dirac equation it is (Equation 8.91) that is normalized. To obtain a
Hermitian Hamiltonian, renormalization is essential and it is this necessity that
is not appreciated in some texts.
Renormalization may be accomplished by introducing a new normalized
two-component wave function x;,:

xX, = M,. (8.106)

The operator V may be determined by requiring the probability density associ-
ated with x, to be the same as that for the four-component wave function y
(Equation 8.91):
Vv = iv. +utb = xix. (8.107)
Substitution for y_ (Equation 8.94), x, (Equation 8.106) and use of Equation
8.96 gives:
N‘*N = 1+ (0.m)K%(o.m)/4m?c’, (8.108)
so that V is the Hermitian operator:

N = [1+ @mK?(o.1)/4m?c?]?
= 14+ (0.m?/8m?c?
+ O(a’). (8.109)
The wave function W), satisfies the time-dependent Schrodinger equation
8.97, but as we have seen the Hamiltonian H is not Hermitian. The new norma-
lized wave function x, satisfies a similar equation:

K'x, = ih(dx,/d0), (8.110)

but the transformed Hamiltonian H’ is expected to be Hermitian. The Hamil-
tonian H” can be related to H by substituting the inverse of Equation 8.106,
v,=N'y,, into Equation 8.97:

HN -'y, II= ih(O(N7x,)/90)

ihN~!(dx,/t) + ih[d/dt, N“"]x,. (8.111)
The Dirac Equation 137

Premultiplication by the operator NV followed by rearrangement now gives

Equation 8.110 with H’ given by:

HK’ = N#N~'—iAN[d/dt,
N“]. (8.112)
To obtain the final Hamiltonian for the positive energy states it only re-
mains to substitute for V (Equation 8.109) and H (Equation 8.105) in Equa-
tion 8.112 and to perform some manipulations. Since N commutes with (o:7)
and the result is only required to be accurate to order mc’a*, we may write:

H' = H +N[—ed, N"] —ihN[a/at, N~"] + O(nc?a®)

H —cN[po + (e/c)d, N'] + O(mc?a°)

H + N[po + (e/e)d, (o.m)"] /8m2c + O(me?a®). (8.113)

Now the commutator involved can be evaluated by noting that:
[Po + (e/c)d, (o-m)*] = [po + (e/c), (o-m)](o-m)
+ (om)[Po + (e/c)d,(o-m)] (8.114)
and using Equation 8.103, so that:

KH’ = KH —(ihe/8m?c?)[(0.E)(o:) + (o.7)(0.E)] + O(mc?a®). (8.115)

The Hamiltonian appropriate to the normalized two-component wave function

x. is thus:
KH’ = —eb+(om)?/2m — (0.m)*/8m3c?
— (ihe/8m?c’)[(¢.E), (o.n)] + O(mc’a®). (8.116)
As anticipated this Hamiltonian is Hermitian. It could now be expanded
further to give a Hamiltonian that may be compared directly with the usual
non-relativistic Hamiltonian, but this is postponed until the Foldy-Wouthuysen
method has been discussed in the next section; in addition the physical inter-
pretation of the individual terms is not given till then.

8.9 The Foldy-Wouthuysen transformation

In this section the positive and negative energy states are decoupled using a
method due to Foldy and Wouthuysen. The non-relativistic Hamiltonian is ob-
tained by a series of unitary transformations, by which the coupling terms are
progressively eliminated. However, before the details of the transformation
are considered it is necessary to look more closely at the properties of the
coupling terms.
138 Advanced Molecular Quantum Mechanics

The Dirac equation may be written as Hy = ih(ow/dt), where y is a four-

component vector and # is the Dirac Hamiltonian:

KH = bmc?—ed+ca.r

= Bmc?+&+0. (8.117)
The symbol & (= — e) represents an even operator, that is one that has no
matrix elements between positive and negative energy components, while ©
(= cam) is an odd operator having only matrix elements between positive and
negative energy components. The term Bmc? is an even operator, but it is ex-
pedient to keep it separate from the other even operator (— e¢@), since they are
of different orders of magnitude. This is also true of the two parts of ca.n, but
keeping them together ensures the gauge invariance of any resulting Hamil-
tonian.
Whether an operator is even or odd is determined by the matrix involved in
its representation. Operators involving 6 or the unit matrix, which are both
diagonal, are even (&), while those involving a,, a, or a, (Equations 8.26) are
odd ((). Other matrices encountered in this chapter can also be classified as
even or odd, o,,, 0, and o, being even and p being odd. The conditions for an
operator to be even or odd can be expressed more formally; an even operator
must commute with 6:
[&,6] = 0, (8.118)
while an odd operator must anticommute with £:

[O, 6], = 0. (8.119)

From these conditions it is easy to show that the product of two even opera-
tors or two odd operators must be even, but that the product of an even opera-
tor with an odd operator is odd. These facts will be used later. Finally, it may
be shown that any operator G can always be broken down into the sum of an
even and an odd operator:

G = 1G + BGB) + (G — BGP); (8.120)

conditions 8.118 and 8.119 show that, since 6” = 1, the first part of Equation
8.120 is even, while the second part is odd.
In the Foldy-Wouthuysen transformation the odd operator © in the Dirac
Hamiltonian (Equation 8.117) is removed by a unitary transformation. Other
odd operators will be introduced by the transformation, but provided it is
chosen correctly, they will be of higher order in a. This process can be re-
peated to eliminate the new odd operators until the Hamiltonian contains no
The Dirac Equation 139

odd operators to the desired order in a; the following discussion is aimed at

a Hamiltonian correct to order mc’a’.
A unitary transformation may be applied to the wave function W to give a
new wave function w’:
wv’ = exp (iS)y, (8.121)
where S is a Hermitian operator and by exp (iS) is meant the power series ex-
pansion:
exp @S) = 1 +78 +(7/21)S? +... =<; (8.122)
the inverse of Equation 8.121 is just ) = exp (— iS)’. The Hamiltonian must
also be transformed and reference to the preceding section and Equations 8.106
and 8.112 in particular shows that the new Hamiltonian is:

H, = exp (iS)H exp (— iS) — ih exp (iS)[0/dt, exp (— iS)]. (8.123)

This may be expanded as a series by substituting Equation 8.122:

KH, II= (1+iS + @7/2)S8?+... KG —iS + 7/28? +...)

—iA(1 + iS + (7/2!)S? +... )[d/at, 1 —iS + (7/28? +... .)]

= H+i(SH —HS) + (77/2!)\S7H — WHS + HS?) +....

— h{[a/dt, S] + (@/2)(S[d/dt, S] — [d/dt, S]S)

+ (i7/2!)(S?[9/dt, S] — 2S[d/dt, S]S + [0/dt, S]S?)/3 +... .}

= KH —Afd/at, S] + i[S, H —4n[d/at, S]]
+:(7 21) Sel —(s)10/01,OI |. : (8.124)
a developing pattern of nested commutators is easily detected if further terms
in this expansion are needed. In the above manipulations it must always be
remembered that S is an operator yet to be specified and must not be assumed
to commute with anything.
If S has the specific form:

S = —iBO/2mc?, (8.125)

the first commutator in Equation 8.124 contributes a term:

i[S, Bmc?] = 3[6O, BI

= 3(6O6— 6°O)
=P 8)
=O, (8.126)
140 Advanced Molecular Quantum Mechanics

where the facts that © anticommutes with 6 (Equation 8.119) and 6? = 1 have
been used. Thus, with this choice of S part of the first commutator cancels the
odd operator appearing in H, the first term of Equation 8.124. Complete sub-
stitution for S and H in Equation 8.124 now gives the transformed Hamiltonian;
in doing this the expressions can be simplified so that 6 only appears linearly
and only terms up to order mca“ are retained, the order being determined on
the basis & ~ mc?a* and © ~ mc’a. The result may be written as:
HK, = Bme?+8&,+O,, (8.127)
where
&, = & + BO’/2mc*— [O, [iha/at—&,O] /8m?c*
— BO*/8mFc§ + O(mc?a°) (8.128)
and
©, = Bliha/at — &,0] /2mc? —O7/3m?c* + O(me’a5). (8.129)
It can be seen that the explicit operators in ©,, the odd part of the transformed
Hamiltonian, are both of order mc’a°. Thus, the odd operator © in the Dirac
equation, which is of order mc’a, has been removed by the transformation at
the expense of introducing odd operators of order mc?a? and higher.
This process may be repeated to remove the new odd operators. That is by
using:
S, = —i8O,/2mce? (8.130)
another transformation may be performed on Equation 8.127 to remove the
odd operator© ;. The resulting Hamiltonian is:
KH, = Bmc?
+ &.+0>, (8.131)
where
& = & + BO?/2mc? — [O, [ihd/dt— &,O]/8m?c4
— BO*/8m3c® + O(mc?a®) (8.132)
and
O2 = O(mc?a*). (8.133)
Only two applications of a unitary transformation have been necessary to re-
duce the Hamiltonian to one in which the largest odd terms are of order me’a°,
and these may be removed by a further unitary transformation to give the
Hamiltonian #3, which is correct to order mc*a‘. This reduced Hamiltonian
H3 operates on the transformed wave function w”. In the subsequent dis-
cussion, the primes and subscripts will be dropped, since it will always be ob-
vious when the Hamiltonian is a non-relativistic approximation to the Dirac
Hamiltonian. However, it should be noted that the wave function appropriate
The Dirac Equation 141

to a non-relativistic approximation is not the same as that corresponding to

the Dirac Hamiltonian; they differ by a unitary transformation. Thus, the
transformed Dirac equation is:

Hy = ih(dy/dr), (8.134)
where
H = Bmc? + & + BO?/2mc? — [O, [ihd/at — &,O] ]/8m2c*
— BO*/8mFc® + O(me7a°). (8.135)
It is now necessary to substitute € =— eg and © = c(am) into Equation
8.135. The first term for which the substitution is not trivial contains
©?, but
we saw earlier (Equations 8.39 to 8.45) that:

(a.n)* = (om) = 1’?+ ehoB. (8.136)

Thus
BO?/2mc? = Bn?/2m + (eh/2m)B(o.B). (8.137)
From this result the term involving
©* is easily seen to be:
— BO*/8m3c& = — Br*/8m3c? — ehB(o.B)n?/4m3c? + O(mc7a®); (8.138)
although the second term in this equation is formally of order mc?a®, its con-
sequences have been observed experimentally and we choose to retain it. For
the remaining term in Equation 8.135, we need:

[iha/at— &,0] [ihd/dt + ed, carr]

II iheca(Vo + dA/dt)

= —iheca, (8.139)

where the electric field E is given by Equation 5.21; this result is similar to
that quoted in the last section (Equation 8.103). Finally:

[O, [in0/at
— &,O]] = —ihec?[(a-m), (a.E)] = — ihec?[(6-m), (0 E)]

= — ihec?[w.E—E.n+io(m,E—E ,t)|

= —Wec?(V.E) + hec’o.(m,E—E,t), (8.140)

where the commutator has been expanded in a similar way to (a.m)* using
Equations 8.39 and 8.40. Substitution of Equations 8.137, 8.138 and 8.140
into Equation 8.135 now gives:
142 Advanced Molecular Quantum Mechanics

KH = Bmc?— ed + Br?/2m + (eh/2m)B(o.B)

+ h?e(V.E)/8mc? — heo.(m , E— E ym) /8m?c?
— Br*/8m3c* — ehB(o.B)n?/4mc* + O(mc’a®). (8.141)
This Hamiltonian still involves four-by-four matrices and operates on a four-
component wave function, but to order mc’as there are no operators connect-
ing positive and negative energy components. Thus, if Equation 8.141 and the
explicit form of the matrix 6 (Equation 8.23) are substituted in Equation
8.134, we obtain two pairs of coupled equations, one for the positive energy
states and one for the negative energy states. The Hamiltonian for the positive
energy states may be obtained from Equation 8.141 simply by replacing B by
+ 1, interpreting the components of o as two-by-two matrices and remember-
ing that it now operates on a two-component wave function. If, in addition,
o is replaced by 2s, the notation of non-relativistic quantum mechanics, the
final Hamiltonian is:

KH = mc?—eot+n?/2m (a)

+ (eh/m)(s.B) (b)
— (eh/4m?c?)s.(r , E—E yt) (c)
(8.142)
— (1/8m3c?)n* — (eh/2m3c?)(s.B)n* — (d)
+ (eh?/8m?c*)(V.E) (e)
+ O(mc?a°).

The appropriate Hamiltonian for the negative energy states may be obtained
from Equation 8.141 by replacing B by — 1.
The Hamiltonian 8.142 for the positive energy states could have been de-
rived using the method of small components. Indeed, the Hamiltonian obtained
by substitution of Equations 8.136 and 8.140 into Equation 8.116 of the
previous section only differs from Equation 8.142 by the rest energy
mc’, but it will be recalled that in the method of small components only the
positive energy states were considered and the energy zero was adjusted. In
fact, the method of small components can also be used to obtain the non-
relativistic Hamiltonian for the negative energy states and there is no reason
to suppose that this method does not give the same results as the Foldy-
Wouthuysen transformation to any order of accuracy; this has been demon-
strated explicitly for the special case of the free electron, for which the posi-
tive and negative energy states can be completely decoupled.
The Dirac Equation 143

The different terms in the non-relativistic approximation (Equation 8.142)

of the Dirac Hamiltonian for the positive energy states may now be identified.
The terms in (a) are, respectively, the rest energy of the electron, the energy
due to the interaction of the charge of the electron with an electric field and
the kinetic energy of the electron. The energy of the interaction of the spin
magnetic moment of the electron with a magnetic field is represented by (b);
this term, which has been encountered already in Section 8.4, is often referred
to as the spin Zeeman term.
The next term (c) is responsible for the interaction of the spin magnetic
moment of the electron with an electric field. This arises because, as we saw in
Section 5.4, an electron which is moving in an inertial frame in which there is
an electric field but no magnetic field, will nevertheless experience a magnetic
field in its own rest frame, and that this magnetic field is perpendicular to the
electric field and the direction of motion of the electron. When the electric
field originates at a nucleus, it is this term that is responsible for spin-orbit
coupling. The classical expression for this term was found in Section 5.10, but
it will be recalled that a simple calculation gives a result that is a factor of two
too large for agreement with experiment, and that the Thomas precession had
to be taken into account; the Dirac equation accounts automatically for the
Thomas correction factor of 5.
The term (d) gives relativistic corrections to the kinetic energy in (a) and
the Zeeman term in (b); the first of these appears in classical relativistic ex-
pressions for the energy. Finally, (e) is the so-called Darwin term which is
peculiar to relativistic quantum mechanics and has no classical analogue; its
origin will become clear when the case of the free electron is considered in de-
tail in the next section.

8.10 The free electron

Although of no chemical interest, a consideration of the free electron provides

an insight into the nature of electron spin and the connection between the
Dirac equation and its non-relativistic approximation. The Foldy-Wouthuysen
transformation is used, since we wish to work with both positive and negative
energy states, although the method of small components could be employed.
However, before doing this we will solve the Dirac equation itself:
Hy = ih(ow/de), (8.143)
where
KH = Bmc?
+ c(a.p). (8.144)

Since H and p commute, the Hamiltonian and the momentum operator

have common eigenfunctions, which may be written:
144 Advanced Molecular Quantum Mechanics

y = u(k) exp [i(k.r

— Et/h)], (8.145)

where /ik and £ are the eigenvalues of p and KH (= ihd/dt), respectively, and
u(k) is a four-component vector, which is independent of the position r. Sub-
stitution in Equation 8.143 gives:

[Bmc* + hc(a.k) — E]u(k) = 0, (8.146)

which is a set of four coupled equations for the components of u(k). Since F
and the components of k are numbers, Equation 8.146 represents an ordinary
eigenvalue problem; by expanding the determinant of the four-by-four matrix
the eigenvalues are found to be:

Es = +(m'c4+ W7k?)3, (8.147)

where each solution occurs twice. This result may be obtained more easily by
multiplying Equation 8.146 on the left by the matrix (Gmc? + hc(a.k) + £),
the resulting matrix being diagonal with all four elements equal to (m?c* +
h’c*k? — E*). The coefficients u(k) may be found by substituting E, back
into Equation 8.146 and as expected the positive energy components predomi-
nate in the positive energy solutions with asmall amount of the negative energy
components mixed in, while the reverse is true for the negative energy solutions.
Thus, even if both the energy and momentum eigenvalues are specified, a
double degeneracy remains and some other operator is necessary to distinguish
between two degenerate solutions. It will be recalled from Section 8.4 that, in
contrast to non-relativistic quantum mechanics, the orbital angular momentum
(r , p) does not commute with the Dirac Hamiltonian, but that the operator
[(r ,p) + sho] does. This implies that the electron has an intrinsic angular mo-
mentum of 5in units of A. Although o does not commute with the Hamiltonian,
its projection on the momentum, (¢.p/p), does and can be used to distinguish
between two solutions with the same energy. The square of this operator is
just unity by Equation 8.40 and hence its eigenvalues are + 1. The two posi-
tive energy solutions of the Dirac equation can then be chosen so that they are
eigenfunctions of (¢.p/p), one with eigenvalue + 1 and the other with eigen-
value — 1; the negative energy solutions can be chosen in a similar fashion. To
obtain the components of u(k) corresponding to these solutions requires some
algebraic manipulation, the inclusion of which here would serve little purpose.
Some peculiarities of the solution of the Dirac equation have already been
noted, in particular the existence of negative energy states and the intrinsic
angular momentum of the electron. However, a still stranger result is obtained,
if the velocity operator is determined. From Equation 1.24 this is given by:

= (dr/dt) = (i/n)(IC,1] = ca: (8.148)

The Dirac Equation 145

this fact was referred to in Section 8.5. Thus the operator appropriate to a
component of the velocity r is proportional to the corresponding component
of a. Now the square of a component of a is equal to unity, so that the eigen-
values of a component of « can only be + 1. This suggests that any determi-
nation of the component of velocity of an electron must give + c, in contrast
to the non-relativistic result that the velocity operator is p/m. This result fur-
ther suggests that the instantaneous speed of the electron can only be 3c, but
the components of a do not commute with one another, so that two compo-
nents of the velocity cannot be precisely measured simultaneously. In addition,
it might be thought that the result that an instantaneous component of velocity
can only be +c is in contradiction to reality, but it should be remembered
that any experimental determination must involve an average over an appreci-
able time interval. Thus, if the electron’s velocity is oscillating very rapidly
about a mean corresponding to the observed value, an instantaneous component
of velocity can still be + c.
This suggestion can be substantiated by considering how the velocity oper-
ator varies with time:

« = (da/dt) = (/A)[H,a] = (2i/h)(cp —aK), (8.149)

where the anticommutation properties (Equation 8.11) have been used. Now
for a free particle H and p are independent of time, so that Equation 8.149
may be treated as a differential equation in a and solved provided the order of
H and «are not changed. Solution of this equation gives:

a(t) = cp! + cpH~'b exp (— 2iHt/h), (8.150)

as can be verified by back substitution; b is a dimensionless integration con-
stant. When it is remembered that the velocity operator is ca, use of Equations
4.38 and 4.39 shows that the first term in Equation 8.150 has the same form
as a classical relativistic expression for velocity. However, the second term is
oscillatory with a frequency of (2H/h); the magnitude of the energy must be
at least mc? so this frequency is at least (2mc?/h), which is of the order of
2X 10” s"1! Thus, the electron has a highly oscillatory motion about amean
position. An experimental determination of the velocity taking much longer
than (h/2mc’) ~ 5 X 10°*s gives a measure of the motion of the mean pos-
ition, but an instantaneous velocity component can still be + c, because of the
presence of the oscillatory term.
Equation 8.150 may be integrated once more to give for the position oper-
ator:
r(t) = atc?H
pt + 5ihe*pb exp (— 21H t/h)H™, (8.151)
146 Advanced Molecular Quantum Mechanics

where a is an integration constant and b is the same constant as before. As well

as the constant and a term with the classical relativistic form, there is again an
oscillatory term with a frequency of at least (2mc?/h). The amplitude of this
oscillation may be estimated by expressing it as:

sih(ca(t) — c?H*p)H™, (8.152)

where Equation 8.150 has been used to eliminate b and the exponential term.
In Equation 8.152 the term in parenthesis has a magnitude of about c, since
ca is the instantaneous velocity operator whose components have eigenvalues
+c, whereas (c*H~'p) corresponds to the velocity that is determined experi-
mentally. Thus, the amplitude (Equation 8.152) of the oscillatory motion is
of the order of (h/mc) = ado ~ 4 X 107’?m, where a is the fine structure con-
stant (Equation 8.85).
We are thus led to the conclusion that the motion of a free electron con-
sists of two parts. The first part is an average motion that can be observed ex-
perimentally. The other part is a highly oscillatory motion that has a frequency
of order (2mc?/h) and an amplitude of order (h/mc). This rapidly varying
motion was given the name Zitterbewegung (literally, trembling motion) by
Schrodinger.
To see how the Zitterbewegung manifests itself in the non-relativistic ap-
proximation of the Dirac equation, the Foldy-Wouthuysen transformation for
a free electron is now considered. It has already been stated that the positive
and negative energy states can be completely decoupled in the special case of
a free electron. This is due to the even operator (& = — e@) being zero when
electromagnetic potentials are absent. In addition, the absence of an external
magnetic potential means that the odd operator (© = cam) has no specific
time dependence so that the operator S in the unitary transformation:

w' = exp (iS) (8.153)

may also be chosen to be specifically time independent; this is still true if there
is a constant magnetic field present and complete separation can also be
achieved in this case. The transformed Hamiltonian (Equation 8.123) now
takes the simpler form:

H' = exp (iS)K exp (— iS). (8.154)

Reference to the previous section now shows that removal of an odd operator
of order mc*a” by a unitary transformation leads to a transformed Hamil-
tonian in which the largest odd operator is of order mc’a”**. The important
thing is that there is only one odd operator of this order, in contrast to the
case of the electron in an electromagnetic field where the number of odd
The Dirac Equation 147

operators increases rapidly with each transformation. Specifically:

O = c(a.p);

O1 = —O0°/3m?7c* + O(me?a) = — («.p)p?/3m?c + O(mc?a!);

O2 = +O°/Smic® + O(nc?a’) = + (@.p)p*/5m*c? + O(mc?a’),

(8.155)
where use has been made of the result:

(a.p)? = p’, (8.156)

which follows from Equations 8.39 and 8.40.
The largest odd operator after n applications of the unitary transformation
is thus:
On = (—1)"@p)p™/[(2n + 1m} (8.157)
and the Hermitian operator S, for the (x + 1)th unitary transformation may
be written as:
5iP(«.p)p (— 1)"(2n ab 1) '(p/me)*"*! (8.158)
Sr —

from Equation 8.125. The presence of the operator p”' should not cause con-
cern, since it will only appear in expressions where it is multiplied by positive
odd powers of p; it isintroduced so that abbreviated notation may be used for
power series in the following manipulations. It is now apparent that the unitary
transformations may be “summed” and applied all at once, the total unitary
operator being:
an [exp (iS,,)] = exp [2 iss): (8.159)

This equality is only true because the operators S,, commute with one another;
if they did not, ambiguities would arise about the order of the operators when
the exponential term was expanded as a power series, and this is one of the
reasons why this technique cannot be used for the case of an electron in a
general electromagnetic field. Thus, the complete removal of odd operators
may be accomplished with one unitary transformation defined by the operator:

S' = Sp = —7i6@p)p Z (— 1)"Qn +1) (piney

— 7iB(a.p)p*f, (8.160)
where =
f = tan\(p/mc) = Ps (—1)"(2n + 1)"(p/mc)*"*" (8.161)

is a function of p only and commutes with « and B.

148 Advanced Molecular Quantum Mechanics

Now S’ can easily be shown to anticommute with the Hamiltonian (Equa-

tion 8.144), so that the transformed Hamiltonian is:

i’ = exp (iS’)H exp (—iS’) = exp ((28')H =(cos(2S") +i sin (28"))K,

(8.162)
as can be confirmed by expanding the exponentials as power series. In addition
(2S')? is equal to f?, since use of the anticommutation properties of B and the
components of @ (Equation 8.11), together with Equations 8.160 and 8.156
shows that:
(2S')? = —pf?[B(@.p)]?
ll + p*f([email protected])”
st fat (8.163)
Since cosine is an even function of its argument:

cos (2S) = cos/f, (8.164)

while for the odd function sine:

sin (2S’) = —iP(@.p)p"' sin f. (8.165)

The transformed Hamiltonian (Equation 8.162) can now be written as:

KH =
II (cos f+ RETR sin f)(6mc? + c(a.p))

B(mc? cos
f + ep sinf)+ mc*(«.p)p"'((p/mc) cos f — sin f).
(8.166)
It only remains to express sinfand cos fin terms of (p/mc). From Equation
8.161, tan f = (p/mc) so that, using trigonometric relations:

cos f= (me/p) sinf = [1 + (p/mco)?]?, (8.167)

and the second term in Equation 8.166, the one involving odd operators,
vanishes. The remaining term involves only even operators so that the com-
pletely decoupled Hamiltonian is:

H’ = Bme*[1 + (p/mc)’] cosf

= Bme?{1 + (pimc)*]?, (8.168)
from Equation 8.167. The Hamiltonian for the positive energy states is ob-
tained by setting B equal to + 1, while substitution of 8 equals — 1 gives the
Hamiltonian for the negative energy states. Consequently Equation 8.168 con-
firms our previous result (Equation 8.147).
The Dirac Equation 149

All this manipulation to obtain a result we already had may seem rather
unnecessary. However, the important thing to note is that when the positive
energy states are decoupled by a unitary transformation (Equation 8.153), all
operators must be subjected to the same transformation, not just the Hamil-
tonian. By determining how operators transform, we will be able to see how
operators before and after the transformation are related to one another; the
description of the electron before the transformation may be referred to as
the Dirac representation, and that after the transformation as the Foldy-
Wouthuysen representation. For example, the momentum operator p is the
same in both representations, since it commutes with S’, but the position
operator rin the Diracrepresentation has for its operator in the Foldy-Wouthuy-
sen representation r’, which is given by:

r = exp (iS’)r exp (— iS’)

Steer (St) + 7/2!) (5S), (Sarit 8, (8.169)
where S’ is given by Equation 8.160. This expression may be expanded, but,
since it involves considerable though straightforward manipulation, only an
outline will be given here. The commutator of S’ and r is first established to be:

[S’,r] = —3hmc*(E,p)
*B(a.p)p + zhp *fB[(@.p)p — pa], (8.170)
where
E, = + [mc*+ c*p?]?. (8.171)
Substitution of Equation 8.170 into Equation 8.169 and evaluation of the
commutators leads to an expression, which may be split up into a number of
summable power series, giving:

r = r—tihp! Basin f— sihp °(E,’mc?—

p' sin f]B(a.p)p
+ in(cos f—1)(o , p)/p?. (8.172)
Finally, substitution for the functions of f (Equation 8.167) gives:

r = r—hihck;
Bat sihc*E, (E, + mc’) '[email protected])p
— tne EE, + me’)(o pp). (8.173)
Once again the appearance of reciprocal operators causes no problems, since
they are merely a shorthand notation for the corresponding power series.
Equation 8.173 shows that the position operator r in the Dirac representation
has, as its operator in the Foldy-Wouthuysen representation, r plus three other
terms, which depend on the momentum operator, thus indicating that the
transformation is a non-local one; that is a point in the Dirac representation
150 Advanced Molecular Quantum Mechanics

is not transformed into a point in the Foldy-Wouthuysen representation, but

into an extended region of space.
In the Foldy-Wouthuysen representation r must represent some new physi-
cal observable which is called the mean position for reasons to become apparent
shortly. In the Dirac representation the mean position has as its operator R,
which is given by:
r = exp (iS’)R exp (— iS’) (8.174)
or
R II exp (— iS’)r exp (iS’). (8.175)
By reference to Equations 8.169 and 8.173 this can be expanded immediately:

R = r+ $ihck; Ba—sihctE;(E, + mc’) 'B(a.p)p

— tne?
ESE, + me?)(6 , p). (8.176)
The determination of the time derivative of R in the Dirac representation
enables this new position operator to be interpreted. From Equation 1.24:

(dR/dt) = (i/A)[H,R] = (i/A)[Bmc? + [email protected]), R], (8.177)

where R is given in Equation 8.176. This can be shown, after some manipu-
lation, to be:
(dR/dt) = KE,*c’p = +c°E,'p, (8.178)
where use is made of the fact that HE,' has the eigenvalue + 1 or — 1, respec-
tively, for positive and negative energy states. Reference to Equation 4.38
now shows that it is R, the mean velocity, which has the classical relativistic
relation to the momentum. Finally, it can be noted that the components of R
commute unlike the components of ca, the operator corresponding to the
time derivative of the position in the Dirac representation.
Thus, there are two important position operators, the Dirac position and
the mean position. It is the latter which is to be identified with the position
operator in non-relativistic theory and is separately defined for positive energy
states. The Dirac position has no classical analogue, since it requires both posi-
tive and negative energy states for its definition. All this agrees with the re-
sults of the earlier part of this section. Equation 8.176 shows that the position
operator r in the Dirac representation consists of two parts, a mean position
R, which is related to the classical concept of position and the motion of which
is experimentally observable, and another part, r—R, which corresponds to
the Zitterbewegung encountered earlier.
The peculiarities involving the angular momentum can also be explained. It
will be recalled from Section 8.3 that the orbital and spin angular momenta
The Dirac Equation |e |

do not commute separately with the Dirac Hamiltonian; that is, they are not
physical observables, although they are in the non-relativistic Schrodinger
treatment. However, the operators (R , p) and = which are given by:

(R ,p) = exp (—iS’)(r y p) exp (iS’) (8.179)

and
= = exp (—iS’)oexp (iS’)

= 0— ick, 'B(a Rp) CEE, + me?)

'p a(o,p) (8.180)

and whose analogues in the Foldy-Wouthuysen representation are (r , P) and

o, do commute with the Dirac Hamiltonian and may be thought of as the
mean orbital angular momentum and the mean spin angular momentum (in
units of 5A). It is, of course, these quantities that are thought of as the orbital
and spin angular momenta in the non-relativistic theory. Finally, we recall
that the total angular momentum, [(r, p) + sho], does commute with the
Dirac Hamiltonian and, as might be expected, combination of Equations 8.173
and:
o’ = exp (iS’)o exp (— iS’)
II o + ick, 'B(a ,p)— cE, (E, + mc?)p ,(e,p), (8.181)
readily shows that it has the same operator form in both the Dirac and Foldy-
Wouthuysen representations.
In the previous section the Foldy-Wouthuysen transformation was applied
to an electron in the presence of external electromagnetic potentials. The
resulting non-relativistic approximation of the Dirac Hamiltonian is correct to
order mc’a°®, and contains a number of terms whose presence can now be ex-
plained in the light of the foregoing discussion for the free electron. In the
Dirac representation the electron interacts with the electromagnetic field at its
position. However, in the Foldy-Wouthuysen representation the electron pos-
ition becomes spread out over a small region around the mean position, and
the electron oscillates very rapidly about this mean position. As we have seen,
the interaction of the electron with the electromagnetic field in the Foldy-
Wouthuysen representation is expressed in terms of r, the mean position, and
consequently correction terms will appear in the non-relativistic approxima-
tion of the Dirac Hamiltonian to allow for the superimposed Zitterbewegung.
The circulation of the electron about its mean position gives rise to both
the intrinsic angular momentum and the intrinsic magnetic moment associated
with the spin of the electron. Indeed a classical model for the Zitterbewegung
may be constructed that gives the correct spin angular momentum for the elec-
tron. At the beginning of this section it was seen that the Zitterbewegung is a
Sz Advanced Molecular Quantum Mechanics

highly oscillatory motion that has a frequency of order 2mc?/h and an ampli-
tude of order A/mc. If we consider an electron moving in a circle of radius
h/2mc with a frequency of 2mc?/h, its velocity must be just c in agreement
with the earlier assertions that the instantaneous value of a component of the
electron’s velocity can only be +c. The angular momentum associated with
this motion is just the product of the linear momentum me and the radius of
the circle A/2mc, so that the intrinsic or spin angular momentum of the
electron is /2 in agreement with experiment. Unfortunately this model cannot
be correct, since, although the electric current associated with this motion
gives rise to an intrinsic magnetic moment, the predicted g factor is unity as
in most classical models.
Except for the Darwin term (Equation 8.142e) all the terms in the non-
relativistic approximation to the Dirac Hamiltonian (Equation 8.142) can now
be understood, since they are related to electron spin or have classical relativ-
istic counterparts. However, the Darwin term may be understood in terms of
the Zitterbewegung, since it is just a correction to the electrostatic interaction
between the electron and the electric potential to allow for the smearing out
of the electron’s charge by the Zitterbewegung.
The position operator r in the Dirac representation has as its operator in the
Foldy-Wouthuysen representation the mean position r plus the oscillatory
term, which will be given the symbol 8. Corresponding to the electrostatic
interaction term — e¢(r) in the Dirac representation is the term — eg(r +8) in
the Foldy-Wouthuysen representation, and this must be averaged over the
Zitterbewegung. Now $(r +8) may be expanded as a Taylor series in § about r:

or +8) = [1+(6.V)+3(6.V)? +... 160), (8.182)

and the time average of this is:

(dr +8)) = (nr) + 34(8.V)*) Hr) +..., (8.183)

since (8) vanishes. The expression ((8.V)*) may be evaluated by expanding it
in terms of vector components and noting that (6;5;)= 6,;(57)/3, so that:

((8.V)*) = (5;V;5 ;V;) = (5,5 V;V;

(57)5,;ViVj/3 = (857)V?/3. (8.184)

Thus, the electrostatic interaction energy in the Dirac representation is given
in the Foldy-Wouthuysen representation by:

—eg(r +8) = —eg(r)— eS) V7G(N)/6+.... (8.185)

Now in the absence of magnetic potentials E = — V@ (Equation 5.21), so
The Dirac Equation 153

that the energy correction due to the Zitterbewegung is just + e(5?)V.E/6;

this agrees with the Darwin term (Equation 8.142e) provided that:

(8?) = 3(h/2mc)’, (8.186)

which is of the order of magnitude one would expect. The agreement is more
striking, if a slowly moving electron (p = 0, £, = mc’) is considered. Equation
8.173 then gives:
8 = —(ih/2mc)Ba, (8.187)

which on squaring becomes:

5° = —(h/2mc)*(Ba).(Ba)
= (h/2mc)?B*a* = 3(h/2mc)’, (8.188)
since B* = 1 and a? = 3 from Equations 8.10.

Bibliography

The Dirac equation

Dirac, P. A. M. (1958), Principles of Quantum Mechanics, Clarendon Press,
Oxford: Chapter 11.
Foldy: pages 4-39.
Rose: in particular Chapters 3 and 4.
Sakurai: Chapter 3 includes the alternative approach to the Dirac equation
mentioned at the end of Section 8.4.

The method of small components

Lowdin, P-O. (1964), ‘Studies in perturbation theory. Part VIII. Separation of
Dirac equation and study of the spin-orbit coupling and Fermi contact
term’, J. Mol. Spectry., 14, 131.
McWeeny, R., > and Sutcliffe, B.T. (1969), Methods of Molecular Quantum
Mechanics, Academic Press, New York: Appendix 4.
The Foldy-Wouthuysen transformation
Foldy, L. L., and Wouthuysen, S. A. (1950), ‘On the Dirac theory of spin x
particles and its non-relativistic limit’, Phys. Rev., 78, 29.
Foldy: pages 15-20.
Rose: pages 87-92 and 123-130.

The relativistic correction (Equation 8.142d) to the spin Zeeman term

Abragam, A., and Van Vleck, J. H. (1953), ‘Theory of the microwave Zeeman
effect in atomic oxygen’, Phys. Rev. 92, 1448.
Atkins, P. W., and Jamieson, A. M. (1967), ‘Perturbation corrections to theg
tensor’, Molec. Phys., 14, 425.
154 Advanced Molecular Quantum Mechanics

Complete separation of the Dirac equation

Case, K. M. (1954), ‘Some generalizations of the Foldy-Wouthuysentransform-
ation’, Phys. Rev., 95, 1323: complete separation for an electron subject
only to a constant magnetic field.
Foldy, L. L.,.and Wouthuysen, S. A. (1950), ‘Onthe Dirac theory of spin 5 par-
ticles and its non-relativistic limit’, Phys. Rev., 78, 29.
Lowdin, P-O. (1964), ‘Studies in perturbation theory. Part VIII. Separation of
Dirac equation and study of the spin-orbit coupling and Fermi contact
term’, J. Mol. Spectry., 14, 131.
Moss, R. E. (1971), ‘The reduction of the Dirac equation to a non-relativistic
form’, Am. J. Phys., 39, 1169: a demonstration that for a free electron the
Foldy-Wouthuysen transformation and the method of small components
are formally equivalent.
Rose: pages 87-88.

Zitterbewegung and the mean position operator

Foldy, L. L., and Wouthuysen, S. A. (1950), ‘On the Dirac theory of spin :
particles and its non-relativistic limit’, Phys. Rev., 78, 29.
Foldy: pages 20-23.
Rose: pages 90-91 and 129-130.
 CHAPTER NINE

The Wave Equation for Many Electrons

Although we now have a suitable wave equation for one electron in the
presence of external electromagnetic fields, we are not yet in a position to
write down the Hamiltonian for a general molecule. In this chapter we move
towards this goal by first considering the problem of just two electrons before
generalizing the theory to the case of many electrons.
In fact, a correct relativistic wave equation for two electrons cannot be
written down in closed form, but it is possible to obtain an approximate Hamil-
tonian provided the kinetic energy of the electrons is very much less than their
rest energy, mc’; this is just the situation that pertains in molecules.
There are a number of possible approaches to this problem of two electrons.
One way is to start with the non-relativistic approximation of the Dirac Hamil-
tonian for each electron. The interaction between the two electrons then arises,
since each contributes to the electromagnetic potentials experienced by the
other. Although this method has a number of associated difficulties, it does
give a physical picture of the origin of the individual terms in the final Hamil-
tonian. A more sophisticated approach is to seek an approximate wave equation
for two electrons, which is the counterpart of the Dirac equation for one elec-
tron. Such an equation is the Breit equation, but to be useful it has to be re-
duced to a non-relativistic form.
Both these approaches give the same non-relativistic approximation to the
Hamiltonian for two electrons, although the policies adopted to circumvent
problems in the first method are chosen to ensure this agreement. Of course,
the most satisfactory approach is to use quantum electrodynamics, but we
content ourselves with noting that the Hamiltonian derived here is the same
as that obtained by Itoh. Even so, it is necessary to include certain radiative
corrections in a phenomenological manner.
155
156 Advanced Molecular Quantum Mechanics

9.1 The electromagnetic potentials due to a moving electron

If the problem of two electrons is approached from the non-relativistic approxi-

mation (Equation 8.142) of the Dirac equation, the electromagnetic potentials
at one electron due to the other are needed. It is the purpose of this section to
obtain them in a suitable form. Before considering their explicit forms it is
necessary to decide how accurately they need to be known in the context of
a molecular environment. This may be done by considering the individual terms
in Equation 8.142, using the results of Section 8.7 andrecalling that the pres-
ent aim is to obtain a Hamiltonian, which is correct to order mc’a’*.
The electrostatic potential ¢ appears as —e@ in 8.142a, so that ¢ is required
to be correct to order mc’a‘/e. The terms 8.142c and 8.142e also involve ¢
through the electric field E, but as they are already small, the scalar potential
only needs to be correct to order mc*a’/e for these terms to be correct to
order mc’a’*.
The largest contribution made by the vector potential is through the terms
8.142b and 1?/2m in 8.142a, and in both cases it must be known to an ac-
curacy of mca3/e. In Section 8.7 we saw that in any case the order of magni-
tude of the vector potentials in a molecule is only mca?/e, so that only the
leading term of any power series expansion ofA will be needed. There are
other smaller terms in Equation 8.142, but these are too small for the vector
potential to make a significant contribution to them.
Now, if the Coulomb gauge is chosen, the potentials due to a charge — e
moving with velocity u are given by Equations 5.73 as:

A — (e/8m€9c?)[u/r + (u.r)r/r?] + O(@ncas/e);

(9.1)
w) — e/4negr + O(mc7a*/e),
where r is the position of the electron relative to the observer; these potentials
are corrected for retardation effects. The expressions 9.1 are not yet in a
suitable form, since they are to be used in a quantum mechanical theory and
should be expressed in terms of momenta rather than velocities. This may be
remedied by replacing u by p/m, since, although they are not strictly equal
(Equation 4.38), the correction terms do not contribute significantly to the
potentials:
A = —(e/8€9mc’)[p/r + (p.n)t/r?] + O(mca/e);
(9.2)
@ = —e/4neor + O(mc7a%/e).
These potentials cannot be used straightforwardly in a quantum mechanical
theory for two electrons, since p and r, which must be interpreted as operators,
do not commute. Thus, the order in which the various factors appear in the
The Wave Equation for Many Electrons Lov

expression for the vector potential is important. The choice may be guided by
insisting that the resulting Hamiltonian for two electrons be Hermitian and
symmetric in the two electrons. By using the order given above these conditions
will be satisfied, but the real justification is that the final Hamiltonian is the
same as that obtained by more sophisticated methods.
The charge of the electron is responsible for the potentials (Equations 9.2),
but the spin magnetic moment of the electron also provides a contribution to
the vector potential and this is found by considering a point magnetic moment,
although it is not clear that this is permissible. As our model we take a slowly
moving particle of charge g and mass m moving in a circle about the origin;
the associated magnetic moment is (see Section 7.1):

w= (q/2mayp) = 2q(a pu), (9.3)

where a, p and u are the position, canonical momentum and velocity of the
particle. The average vector potential at position r, where r is very much larger
than a, may be expressed in terms of yp. The vector potential due to a point
magnetic moment is then obtained in the limit that a vanishes.
For simplicity Equations 5.72 rather than Equations 5.73 are used for the
vector potential in this model, since the gauge may always be adjusted later if
desired. Now for a slowly moving particle:

A = qu/4neoc?|r —al, (9.4)

and this may be expanded as a power series in a about r by noting that for any
function f(r — a):
Sita fit) a. Vit) a (9.5)

so that using Equation 2.78:

1/|r—al reaVELir)
he

Il Urania (9.6)

Substitution in Equation 9.4 followed by rearrangement now gives:

A II (q/4neoc’)[u/r + u(a.n/re t+...)

\| (q/4me€oc”)[(d/dt)(a/r + a(a.r)/2r?)
+ 2(u(a.r) — a(u.r))/r? +... ], (9.7)

where use has been made of the facts that u = da/dt and r is a constant vector.
Equation 9.7 gives the instantaneous potential at position r. When the aver-
age is taken the first term vanishes, since it is the time derivative of a periodic
158 Advanced Molecular Quantum Mechanics

function; this may easily be checked explicitly for the model employed here.
The remainder of Equation 9.7 may be written in terms of w by noting that
from Equation 2.38:
(a,u),r = u(a.r)— a(un), (9.8)

so that the average vector potential is:

A = (1/4necc*)(a,nirt.... (9.9)
When a is allowed to tend to zero, the vector potential at a position r relative
to a constant magnetic moment yp is obtained:

A = (1/4m€9c?)(u, 1)/P°. (9.10)

In the case of the electron the spin magnetic moment is (Equation 8.49)
u = — (eh/m)s, so that the associated vector potential is:

A = —(eh/4negmc’\(s , 1)/r°. (9.11)

This potential satisfies the Coulomb gauge condition (Equation 5.35), since
it is divergenceless. In a molecular environment it is of order mea?/e, confirm-
ing the assertion made in Section 8.7.
The vector potential due to a spin magnetic moment is taken to have the
form of Equation 9.11. However, one might expect that in a frame in which
the electron is moving the observed vector potential will not quite be as given
in Equation 9.11 and, in addition, a small scalar potential will be experienced.
The correction to the vector potential is of order mca°/e and may safely be
ignored as may retardation effects, but the associated electric potential, which
is given approximately by u.A, is of order mc’a*/e and cannot be neglected.
This contribution to the total scalar potential is:

o = —(eh/4negm’c’)s.(r y p)/r?. (9.12)

It will be seen later that, if this contribution is included, agreement is not ob-
tained with the Hamiltonian derived from the Breit equation later in this chap-
ter. It is necessary to argue that a classical model for the spin magnetic moment
is not quite appropriate and that this refinement should be ignored. This is a
further difficulty associated with the present approach to the problem of two
electrons.
The total potentials, A; and ¢;, at an electron i in the presence of a second
electron 7 may now be written down to the desired accuracy (subject to the
remarks of the previous paragraph). In doing this the vector:

By Fleas (9.13)
The Wave Equation for Many Electrons bog

is introduced; it is noted that rin Equation 9.11 is just r;;, but that rin Equa-
tions 9.2 is —r,;. In addition, the subscripts are added to the charges and
masses ofthe electrons, so that the origin of the terms in the final Hamiltonian
may be seen more easily. If A and ¢ are now the external potentials:

A; A (e;/8m€gmjc’) [p;/r;; 4h (pj-rij) ti; /77)]

— (e;h/4negmjc’)\(s; Atiyltiy) ak O(mc*/e) (9.14)

and
$; = ¢—e;/4n€or;; + O(mc’a‘/e); (9.15)

these potentials satisfy the Coulomb gauge. Although the highest neglected
terms in the expression for the vector potential are formally of order mca‘/e,
we have only taken Equation 9.14 to be correct to the required accuracy of
mca?/e, because of the uncertainties involved in this derivation of the Hamil-
tonian. Similarly the scalar potential (Equation 9.15) has only been assumed
to be correct to order mc’a4/e.

9.2 The Hamiltonian for two electrons

The non-relativistic approximation to the Dirac equation for an electron 7 is

Hy = ihow/dt, where (Equation 8.142):

H, = mjc’ — ed; + 1j/2m; (a)

+ (e;h/m;)(s;.B;) (b)

— (eh/4mjc’)s;.(r, , Ej; — E; x7) (c) (0.16)

— (1/8mjec?)\n}—(eh/2mic*)\(s;.B;)n; (4)
+ (e;h?/8mjc?)(V.E;) (e)
+ O(mc’a®)
and the wave function y has two components.
For two electrons the Hamiltonian can be written as:

H=H,+H, = (2 ts (9.17)

where each electron contributes to the potentials experienced by the other,

that is the potentials ex perienced by electron i are given by Equations 9.14 and
9.15. The wave function associated with this Hamiltonian has four com-
ponents, since each electron has two possible spin orientations.
All that is necessary is to substitute for the potentials, and simplify the
160 Advanced Molecular Quantum Mechanics

resulting terms, so that in the final Hamiltonian any potentials that appear are
just the external potentials. However, at this stage a further difficulty appears,
since for any effect that one electron has on the other there will be a recipro-
cal effect, and a decision has to be made as to which interactions should be
counted twice and which should not. That some interactions should only be
counted once, may be seen by referring to Section 5.9. There the Lagrangian
(Equation 5.76) for one charged particle contains terms arising from the inter-
action of its charge with the potentials due to the charge of another particle.
However, in the Lagrangian (Equation 5.77) for both particles together these
same terms appear once, not twice, since the interaction is symmetric between
the two particles. If the Lagrangians for the individual particles had been added
together a correction factor of ;would have been needed in these interaction
terms. Similar remarks apply to the corresponding Hamiltonians. In deciding
which interaction terms should only be counted once (or which should have
correction factors of +), we may be guided by their symmetry with respect to
interchange of the two particles, but the ultimate decision will be made so that
agreement with other methods is achieved.
For simplicity it is supposed that the external potentials, A and @, vanish,
since they can be reintroduced later by the usual replacement:

py = 9p, © eS H KH + & e;¢. (9.18)

The influence of the scalar potentials due to the electrons is discussed first.
The term — e;¢; in 9.16a makes a contribution:

€1€2/4 €or 12 (9.19)

for each of the electrons. This is the usual Coulomb interaction term, and
being symmetric between the two electrons should only be counted once, as
is confirmed by the non-quantum-mechanical theory in Section 5.9.
This scalar potential also makes a significant contribution through the elec-
tric field E; in the terms 9.16c and 9.16e. Of course the electric field also de
pends on the vector potential (Equation 5.21), but this contribution is
negligible, so that:
E; = —V¢;—0A,/dt = V(e;/47€or;;). (9.20)
Now, since V operates on the position of electron i only, Equation 2.78 shows
that:
E; = — (e;/4me€o)1;;/r3;. (9.21)
In the term 9.16c the vector potential also appears by virtue of the presence
of 7, but again the contribution is negligible.
The Wave Equation for Many Electrons 161

Hence the contribution of the term 9.16c to , due to the presence of

electron 2 is:

(€1¢2h/16m€gmjc?)s;.[pi , (ti2/ri2)— (12/92) , pi] + O(me?a’). (9.22)

This may be simplified by noting that p, A(t12/ri2) is just equal to
= (r12/r}2), Pi, as may easily be shown using the techniques of Chapter 2 and
in particular Equation 2.96. There is a similar contribution to H due to the
presence of electron 1 and, since each of these terms is not symmetric between
the two electrons, they must both be counted. The total contribution of the
term 9.16c to the Hamiltonian for two electrons is thus:

i (e:e2h/8m€9c7r}2)[s1 (typ A pi)/m} — $2.(112 A p2)/m3] + O(mc’a*), (9.23)

since f2; = —fy2 (Equation 9.13). This expression represents the spin-orbit
interaction, which is the interaction between the spin and orbital motion of
the same electron. It arises from the electric field produced by the other elec-
tron, since by virtue of its motion the electron experiences a magnetic field
which interacts with its spin magnetic moment.
The term 9.16e may be dealt with more easily, since from Equations
OD eand:2:95:

V.E; — — (e;/4m€o)V (1; ;/73;) = — (€;/€0)6(1;;)- (9.24)

Again it is clear that each of the two possible contributions to the Hamiltonian
is not symmetric between the two electrons and that both must be counted,
so that the term 9.16e is responsible for:

— (€1€2h?/8€9c7)5(r 2)(1/mz + 1/mz) + O(c’). (9.25)

This term is similar to the Darwin term (8.142e), which is a correction to the
interaction of the charge of an electron with an electric field due to the Zitter-
bewegung; in this case the other electron is responsible for the electric field.
All the significant terms that arise from the scalar potentials of the electrons
have now been considered. It has already been noted that the vector potentials
of the electrons only contribute significantly to the final Hamiltonian through
the term 9.16b and the term 7?/2m; in 9.16a. For potentials that satisfy the
Coulomb gauge condition this latter term can be expanded (Equation 7.14):

m?/2m; = p?/2m; + e;A;.p;/m; + e7A; /2m;; (9.26)

the last term is negligible and only the middle term need be considered further.
The orbital parts of the vector potentials due to electrons 2 and 1 give rise to
similar terms when substituted in H , and H2, respectively. Hence, as is indicated
162 Advanced Molecular Quantum Mechanics

by the non-quantal theory of Section 5.9, this contribution to the Hamil-

tonian should only be counted once:

, (€1¢2/8meomymzc’)[p1.(7i2P2) i (pity) -P2)] ar O(mc? a®). (9.27)

In the present approach there is no way of determining the correct order of

operators in this expression, although it can be required to be Hermitian and
symmetric to interchange of the two electrons. Both these conditions are satis-
fied by the term 9.27 and it will be seen later that the order of the operators
as written here is in fact correct. The interpretation of the term 9.27 is that it
represents the interaction of one electron with the magnetic field produced by
the orbital motion of the other and vice versa; it is referred to as the orbit-
orbit interaction and includes a correction for retardation.
The vector potential due to the spin of electron j provides, through the
second term in Equation 9.26, a contribution:

— (ee;h/4neqmymjc?)(s; y ¥;j/73)).pi + O(mc7a*). (9.28)

Since it is the spin of 7 but the momentum of / that appears in this term, it is
not symmetric between the two electrons, so that the total contribution to the
Hamiltonian is:

+ (€;€2h/4me9m mcr) [S1-(12 \ P2) — S.(ri2 A Pi] + O(mc’a°*). (9.29)

This represents a spin-other-orbit interaction, since one electron interacts with

the magnetic field produced by the spin of the other.
Finally the term 9.16b must be considered and for this the magnetic field
at electron i due to electron j is needed; from Equation 5.20 it is given by
B; = V , Aj. Direct use of the orbital part of Equation 9.14 together with
liberal use of the techniques of Chapter 2 shows that the orbital contribution
to this magnetic field is:
(e;/4m€omjc?r};
(ti; , Pj): (9.30)
This result may be obtained more easily by using Equations 5.72 instead of
Equations 5.73, since these are related by a gauge transformation and only
differ by the gradient of a scalar, the contribution of which to the field
vanishes because the curl of a gradient is zero (Equation 2.70).
The spin contribution to B; is:

x (e;h/4ne9mjc” )V NGa 1;;)/r3;, (9.51)

where V operates on the position of electron i. Use of Equation 2.68 shows
that:
V A (s; ANTI; = sjV.(1;;/r3;) — (8;.-V)x/73, > (9.32)
The Wave Equation for Many Electrons 163

since s; and V commute. The first term is just 475(1;;)s; from Equation 2.95,
while the second term may be evaluated using Equation 2.96:

(s; V)r;/r3; = (41/3)8(r;;)s; te s;/r3, = 3(s;.nijtij/Ti, (9.33)

whereitshould be remembered that in the present context the subscripts iand

j tefer to electrons not vector components. The contribution of the spin mag-
netic moment of electron 7to the magnetic field at electron is thus:

— (e;h/4n€omjc’)[(87/3)5
(r;;)8; — s,[r}, + 3(s;-xitij/ris]. (9.34)

When the orbital part (9.30) of B; is substituted into 9.16b, two different
terms arise, one for each electron, so that the contribution to the Hamiltonian
is:

ao (€:€2h/4€9m m2C7Fi2) [si.(ti2 A P2) — 82(112 A pi] + O(mc’*a*). (9.35)

This term is the same as 9.29 and provides another contribution to the spin-
other-orbit interaction. In this case the spin of each electron interacts with the
magnetic field produced by the orbital motion of the other, whereas the
term 9.29 is interpreted as being due to the motion of each electron in the
presence of the magnetic field due to the spin of the other. It may be argued
that these two interactions are really one and the same and that only one of
the terms, 9.29 and 9.35, should be counted. This is in fact necessary if agree-
ment is to be obtained with the Hamiltonian obtained from the Breit equation.
Finally, the spin part (9.34) of B; must be substituted into 9.16b and for
each electron an identical term arises, which is consequently only included
once in the final Hamiltonian:

+(e 1e2h?/4m€9m m2C7) [(s1.S2)/r 2 — 3(81.62)(112-S2)/r r)

— (81/3)5(112)(81-82)] + O(mc7a*). (9.36)

This arises from the interaction of the spin magnetic moment of each electron
with the magnetic field of the spin magnetic moment of the other. It thus
represents the spin-spin interaction, the first two terms in 9.36 being ana-
logous to the classical dipole-dipole interaction, while the term involving the
Dirac delta function represents a Fermi-contact-type interaction for which the
two electrons must coincide.
All the significant interaction terms in the two-electron Hamiltonian have
now been derived. They represent the Coulomb (9.19), the orbit-orbit (9.27),
the spin-orbit (9.23), the spin-other-orbit (9.29 and 9.35) and the spin-spin
(9.36) interactions; in addition there is a term (9.25) that is analogous to the
Darwin term in the one-electron Hamiltonian. If external electromagnetic
164 Advanced Molecular Quantum Mechanics

fields are reintroduced by the replacements 9.18, the total Hamiltonian for
two electrons is given by:

iC ae jlmic’ — e,6; + 17/2m; + (eh/m;)(s;-B;)

— (e;h/4mjc’)s,.cn; , E; — Ej.) — C1 [8mjc?)n?

— (e;h/2mpc?)(s;.B,)n} + (e;h?/8mic? (V-E;)]

+ (ee /47€ 0712)

— (ee,/87€9m4my¢7) [Ty .(r}2m™m) + (M12)

713 (t12-™)]

= (€:¢2h/8m€9c7rj2) [si-(t12 , m)/Mj— S(t Am™2)/m3 |

+ (€,¢,h/4m€9mym2C7r}2) [S1-(P12 To) — S2-(T12 , ™)I

+ (€,€h/4me9m
myc’) [(81.82)/ri2 — 3(81-T12)(F 12-82) /Ti2

— (81/3)5(112 (81-82 )]

— (€;€2h?/8e9c7)5(t1)(1/mi + 1/m3) + O(nc?a*). (9.37)

The potentials ¢; and A; and the fields E; and B; at electron 7 are now due en-
tirely to external sources and not to the other electron.
In Equation 9.37 only one ofthe two contributions (9.29 and 9.35) to the
spin-other-orbit interaction has been included. It is recalled that another diffi-
culty associated with this method involves the order of the operators in the
orbit-orbit interaction. In addition, the contribution (Equation 9.12) of the
spin magnetic moment of one electron to the scalar potential at another has
been omitted;ifit had been retained there would have been an additional term
in Equation 9.37 equal to twice the spin-orbit term (9.23). For these reasons
this approach is not entirely satisfactory, but it does have the advantage that
it exhibits the origin of each term in the Hamiltonian and allows a physical
interpretation to be given to each.

9.3 The Breit equation

In the previous section a non-relativistic approximation to the Hamiltonian

for two electrons was sought by starting with the non-relativistic approxima-
tion to the Dirac Hamiltonian. We now enquire whether it is possible to write
down a relativistic Hamiltonian for two electrons.
Such a Hamiltonian would be expected to have the form:
The Wave Equation for Many Electrons 165

H —— Hy tH + Hi, (9.38)

where 4; is the Dirac Hamiltonian for electron 7:

KH; = B;m;c* = CQ; .1T; — €;9; (9.39)

and #2 is an appropriate interaction term. The corresponding wave function

has sixteen components, since the wave function for a single electron has four
components. This means that the operators in the Hamiltonian (Equation 9.38)
are represented by matrices of order sixteen and, for example, the Dirac oper-
ators 8; anda; in Equation 9.39 are now to be thought of as an appropriate
direct product of 8 and @ with the unit matrix (see the next section). Conse-
quently a relativistic wave equation for two electrons is rather complicated
but one might expect it to be reducible to a non-relativistic form appropriate
to two electrons that are both in positive energy states; the associated wave
function would then have four cpmponents, since there are two spin orienta-
tions for each electron.
The form of the interaction term #2 in the Hamiltonian (Equation 9.38)
must now be considered. As a leading term one would expect the Coulomb
interaction, but a Hamiltonian:

da — Hy te KH, a6 (€1€2/47€ or 12) (9.40)

cannot be correct, since the wave equation with this Hamiltonian is not even
approximately Lorentz invariant. The correction terms can only be obtained
rigorously by using quantum electrodynamics. In principle they may be ob-
tained to any order of accuracy, but in practice they can only be obtained ap-
proximately. It is beyond the scope of this book to go into the details, but
essentially second-order perturbation theory is used to describe the emission
of a virtual photon by one electron and its absorption by the other and vice
versa; to do this the eigenvalues and eigenfunctions of the approximate Hamil-
tonian (Equation 9.40) are used. The result is an additional interaction term:

— (€ €2/87€
oF12)[(a1 2) + (@1 1 12)(42-0 2)/ria] > (9.41)

which is known as the Breit operator. Because perturbation theory is used and
because of the approximations involved in its derivation, this operator must
only be used for slowly moving electrons and then only in first order. The mat-
rix representation of the operator (Equation 9.41) also involves matrices of
order 16; in this case they are related to direct products of the matrix repre-
sentations of the components of the Dirac operators a, anda.
Although we are not ina position to derive the Breit operator, it can be seen
that it is approximately correct by referring to the classical (non-quantum-
166 Advanced Molecular Quantum Mechanics

mechanical) Hamiltonian for two electrons, that was derived in Section 5.9.
Equation 5.81 shows that the classical interaction Hamiltonian consists of the
Coulomb term together with:

i (€ 1e2/87€9M M27 12C7) [(P1-P2) of (p1-¥12)(P2-F12)/Ti2] (9.42)

or in terms of the electrons’ velocities, u, and uy:

ap (€1€2/87€or12c7) [Cu U2) + (Uy .F12)(U2 Ip)/Fa]. (9.43)

This is a classical expression and in going over to a relativistic quantum mech-

anical theory it is appropriate to replace the velocity u; of electron i by its
Dirac velocity operator ca; (Equation 8.148). With this replacement, 9.43
becomes identical to the operator 9.41.
The Breit equation is thus Hy = iA(dW/dt) with the Breit Hamiltonian
given by:

H = Hy, +H, + (€1€2/4m€

oF12)
aa (e 1€2/87€F 12) [(a; a>) aF (« 1 1 12)(G2 I2)/ri2] af O(mc’a*),
(9 44)

where #; is the Dirac Hamiltonian for electron i (Equation 9.39). It is clear

that like the Dirac equation the Breit equation is gauge invariant, since it can
be written in terms of the operators 7; and (ihd/dt + & e;9;) (see Section 7.2).
Although both the Coulomb term and the Breit Operator are formally of
order mc’a? in a molecular environment, the Breit Hamiltonian (Equation
9.44) is in fact correct to order mca‘. It must be emphasized that it is an ap-
proximate Hamiltonian, since it is not Lorentz invariant and the effects of
quantum electrodynamics have been introduced using perturbation theory.
Again we note that because of this the Breit operator should only be used to
first order in any application. In addition, the Breit equation should only be
used for electrons moving with velocities much less than the speed of light.

9.4 Reduction of the Breit equation to non-relativistic form

It is appropriate to reduce the Breit equation to a non-relativistic form, since

it is only valid for electrons with low velocities. In addition, a four-component
equation is more convenient than one with sixteen components and the result-
ing Hamiltonian can be treated with well-established techniques. Both the
method of small components (Section 8.8) and a Foldy-Wouthuysen-type re-
duction may be used, but the latter has attracted more attention and, being
more straightforward, it is this approach that is presented here.
As might be imagined the labour involved is considerably greater than that
The Wave Equation for Many Electrons 167

needed for the reduction of the Dirac equation and only an outline of the
method is given. For simplicity the time-independent problem is discussed,
but there is no reason to suppose that the time-dependent Hamiltonian does
not have the same form.
In the Foldy-Wouthuysen reduction (Section 8.9) of the Dirac equation
the operators in the Dirac Hamiltonian are classified as even (&) or odd (©)
depending on whether they have no matrix elements or only matrix elements
between the positive and negative energy components of the wave function.
More formally even operators commute and odd operators anticommute with
the Dirac operator 8. The odd operators are removed progressively by the ap-
plication of a sequence of unitary transformations.
A more complicated classification of operators must be used for two elec-
trons, since the wave function has sixteen components, which cannot be
labelled simply as positive or negative energy components. However, the wave
function can be written as:
Wa4

y= We (9.45)

where, for example, Y,, has four components for which both electrons have
positive energy, while for y,- electron 1 has positive energy but electron 2
has negative energy. We are interested in decoupling Y,, from ,-, Y_, and
W__ to obtain a four-component Hamiltonian for two electrons, which both
have positive energy; this Hamiltonian is required to be correct to order mc7a*.
It will be seen that the Breit Hamiltonian (Equation 9.44) can now be
written:
H = Bym,c? + Bymyc? + (&8) + (80) + O©&)+ (OO). (9.46)
by analogy with Equation 8.117. This is just an extension of the Foldy-
Wouthuysen notation, so that, for example, an even-even operator (&&) such
as B, or B> is even with respect to both electrons 1 and 2. On the other hand
the components of «2 are even-odd operators (&O) and are even and odd with
respect to electrons 1 and 2, respectively. As a further illustration, y,, is only
connected with y_, by an odd-even operator (O&).
These operators may be defined more formally. For an operator to be even
with respect to electron 1 it must commute with B,, but if it anticommutes
with B, it is odd with respect to electron 1. Thus:
168 Advanced Molecular Quantum Mechanics

II II
[((G&), Bi] lI ((&0), 61] lI [(G&), Ba] [(O&),Bo] 0;
(9.47)
[O&), 61]. = (OO), Bi], = [(&O), B21. = [OO), Bel.
It is now easy to show that the product of say an odd-even operator with an
odd-odd operator gives an even-odd operator:

(O&)OO) = (&0) (9.48)

and so on. With these definitions the various Dirac operators can now be classi-
fied:

(&&): B,,B., the 16 X 16 unit matrix;

(9.49)
(& ©): O25 > Ary > A, 5

O&): Aix, Aiy, Xz;

(OO): any product of a component of a, with a component ofa>.

All these assertions may be checked explicitly. With the choice of wave
function (Equation 9.45) the matrix representation of the Dirac operators for
electron | are:

10 pee ee) Oe pOs ps0) eal.

Orrat Aaa NeiG Garo Olgas;
Bi = 5 ene jc a Ffad | em lei (9.50)

Omnis Olen. Oleh OnicakanOmaG

where each element is itself a four-by-four matrix and in particular, if e,, e,
and e, are unit orthogonal vectors:

e; 0 (eo Te,) 0
0 e 0 (e =re,)
ae . (9.51)
(e, Flee) 0) =e; (9)

0 (Guat Les) 0 ee

The corresponding matrices for electron 2 are:

ieee ah Oo 04 venOrhiO
Oat? BONN Oo «Ole Ot a
By = iene , (9.52)
OO Mieeare bleed Clowmed.(Piaiea ts
The Wave Equation for Many Electrons 169

where

a. te. Te.) 0 0

( 2 re.) —e, 0) 0
c— (9.53)
0 0 ez (e, — iey)

0 0 (e,- 1 ie,) cy

These matrix representations satisfy all the relationships they are expected to.
The operators 8; and the components ofa; all anticommute with one another
and the square of each is the unit matrix of order sixteen. In addition, 6, and
the components of @, all commute with 6, and the components of a, as they
must, since they operate on different electrons.
We are now in a position to identify the operators in Equation 9.46:

(G&) = — e161 — e262 + €1€2/47

€or 12~ mc°o ;

(80) = ca.m ~ mca;

(O8) = cay.m
~ me’a; Cy

(OO) = —(e1€2/87€07 12) [(@-02) + (@ 1-812)(@2-F2)/r2] ~ me?a?.

From this identification it is clear that:

[(&0), ©&)] = 0; [(&&), OO)] = 0, (9.55)

commutation relations that are useful in the subsequent development.
With these preliminaries settled, we may return to the original problem of
reducing to non-relativistic form the Hamiltonian (Equation 9.46), which oper-
ates on the wave function (Equation 9.45). To achieve this, unwanted operators
are removed by the Foldy-Wouthuysen method of subjecting the wave function
to a unitary transformation:
y' = exp (iS). (9.56)
At the same time the Hamiltonian is modified and for the time-independent
problem the transformed Hamiltonian is, from Equations 8.123 and 8.124:
H, = exp (iS)H exp (— iS)

= 5d Sede). fo) (Sas AC] |are (9.57)

This transformation introduces new undesirable operators into the Hamil-
tonian, but, if the Hermitian operator S is correctly chosen, these are formally
smaller than the operators removed. This procedure is repeated until the
Hamiltonian is correct to the desired accuracy, in this case mc7a’*.
t72 Advanced Molecular Quantum Mechanics

Although Equation 9.62 is the simplest acceptable choice for S, its substi-
tution in Equation 9.57 and the subsequent expansion is quite laborious even
when the commutation relations 9.55 are used; consequently only the result
is given here. Two applications of the transformation are necessary to obtain
a Hamiltonian, which is of the desired type and correct to order mc’a*. The
order of magnitude of the terms is estimated on the basis (Equations 9.54)
that the (&&) and (OO) operators in Equation 9.46 are of order mc7a’, while
the (©) and (O&) operators are both of order mc7a. The result is:

H, = Bymc? + B,mc? + (&8&) + B(O8&)?/2m,c? + B(&O)?/2m2c?

— B (O8&)*/8m3c* — Bx(&O)*/8m3c> — [(O8), [(O&), (&&)] ]/8mIc*
— [(&O), [(&O), (&&)] ]/8mic*
+B:B2[(&O), [(O&),OO)].]./4m wn2c4
+ (By + B2(QO)/4(m1 + mz)c? + (1 — B1B2(OO),/2 + O(ne’a*).
(9.65)
All the operators in this transformed Hamiltonian are of the even-even type
except for the last, which is odd-odd and involves (OO),, the sum of ©) and
other odd-odd operators introduced by the first unitary transformation.
The penultimate term in Equation 9.65 contains (OO©)*, but (OC) is just
the Breit operator and it has already been emphasized that it must only be
used to first order; in fact retention of this term leads to discrepancies between
theory and experiment for the atomic spectrum of helium. When this term is
omitted and 6, and B are set equal to the four-by-four unit matrix, we obtain
the four-component Hamiltonian appropriate to two electrons, which both
have positive energy:

H = mc? + mc* + (&8) + O8&)7/2m,c? + (80)?/2m,c?

— ©&)*/8mic® — (&0)*/8m3c° — [O8), [O&), (&&)] ]/8mict

— [(&O), [(&O), (&&)] ]/8m3c* + [(&O), (©&),
OO .]./4mim2c*
+ O(mc’a'), (9.66)
where the subscript has been dropped from H.
Of course the explicit forms of the operators (&&), (0), (O&) and (OO)
given in Equations 9.54 must now be substituted into Equation 9.66. Some of
the work has already been done, since reference to Equations 8.137 and 8.138
shows that:
O&)/2myc? = wi/2m, + (e,h/2m,)\(6,.B,) (9.67)
The Wave Equation for Many Electrons bys

and

+ O(mce’a’),
—(O&)*/8mic> = — (1/8m3c?)4 — (ef/4m3c?)(o,.B, )7?
(9.68)
with similar expressions for the terms involving (0)? and (&0)*. However,
the remaining terms are more complicated, but liberal use of the techniques
of Chapter 2 and relationssuch as Equation 8.40 shows quite straightforwardly
that:

— [©&), [(O&), (@&)] ]/8mic* = (e,h?/8mic?)(V.E))

— (e;h/8mic?)o,.[m, ,E:—E1 , 71]
— (€:€2h/16m€9c7r}2)01.(r12, ™)/m}

— (€ :€2h7/8€qc7)5(t12)/m}, (9.69)
with a similar expression for the term involving [(&O), [(&O), (&&)] ] except
that the subscripts 1 and 2 are interchanged. With even more labour it may also
be shown that:

+ [(@0), [(O&), OO). ]./471m2c4

= (€1€2/8me9mymgc?)[m.(ri2™ )+ (My -F12)
713 (T12-™)]
+ (ee, h/8m€9mymzC7r}2)[01.(F12 2) — 82-(Ti2 pT)
+ (€€)h?/1 679m 1m2C7) [(61.02)/7?, — 3(01-812)(t12-02) [Fin
— (82/3)6(112)(0;.02)]. (9.70)

The final Hamiltonian may now be assembled by substituting Equations

9.54 and 9.67 to 9.70 into Equation 9.66:

De iene
i=1 lnie? — e6; + 1?/2m, + (eh/2m;)(6;.B;)
— (e;h/8m}c?)o;. [m; , E; — E; ,mi] — (1/8mpec?)n?
— (e;h/4mjc?)(o;.B;) 1? + (e;h?/8mjc? (V.E;)]
+ (€1€2/47€o712)

— (€,€)/8m€9m4m2.c7) [mr(712782) + (1-112)

713. (F122)|
— (€,€,h/16m€9c7ry)
[01-(t12 ,81)/Mj — 92.(F12aTt2)/m3]

ts(€,e,h/8megmymMyzC7F}2) [01 (112 AT) — 87 .(t1 aT™)]

174 Advanced Molecular Quantum Mechanics

es (e,e,h?/16me9m mC’) [(01.02)/ri2 — 3(6,.4 (tr 02)/ri2

— (87/3)6 (r12)(1.02)]

— (€,€,h?/8€qc”)5(r12)(1/m32 + 1/m3) + O(mc?a*). (9.71)

This Hamiltonian is identical to that obtained in Section 9.2, since it is re-
called that 0; has been replaced by 2s; in Equation 9.37. However, in deriving
the Hamiltonian (Equation 9.37) certain problems were resolved by insisting
that there should be eventual agreement with Equation 9.71. The advantage
of the method of Section 9.2 is that the physical significance of the individual
terms is quite clear from the way in which they are derived. In the present
method the origin of some of the terms is not obvious and the amount of
labour involved is substantial, but it is free of the objections to the method of
Section 9.2. Finally we again note that the same Hamiltonian has been ob-
tained using quantum electrodynamics.

9.5 Radiative corrections

The Dirac equation for the electron predicts a spin magnetic moment of
—(eh/2m)e and a spin angular momentum of she (Section 8.4). The g factor
of the electron is the ratio of the magnitude of these two quantities measured
in units of (e/2m). Consequently the Dirac equation leads to a g factor for the
electron of exactly 2.
The transition to the notation of non-relativistic quantum theory can be
made by replacing o by 2s. This has been done in Equations 8.142 and 9.37,
which are the non-relativistic approximations of the Dirac and Breit Hamil-
tonians, respectively. Now in these approximate Hamiltonians each of the terms
involving the spin of an electron arises by virtue of its spin magnetic moment;
the spin angular momentum does not appear as such in the Hamiltonian. Thus,
rather than replace o by 2s, we could have replaced the spin magnetic moment
of the electron, —(eh/2m)o, by — g(eh/2m)s, where g is exactly 2. Since
(eh/2m) is just the Bohr magneton pg, this replacement may be written:

— (eh/2m)o— — gugs. (9.72)

When Dirac first put forward his theory, the experimental value of the g
factor was also 2. However, since then experiment has shown that it differs
slightly but significantly from 2. It is now one of the most accurately known
constants and one of the more recent experimental determinations gives it as:

g = 2:002 319315 (+7 X 107°). (9.73)

The Wave Equation for Many Electrons LS

The discrepancy between Dirac theory and experiment is attributed to quan-

tum electrodynamic effects, one of the latest theoretical estimates being
2:002319312 (+3 X 10°’) in good agreement with the experimental value
(Equation 9.73); the error is due to uncertainty in the experimental value of
the fine structure constant (see later). Since it is not possible to go into the
details here, the quantum electrodynamic correction to the electron’s g fac-
tor is included phenomenologically. Thus the replacement 9.72 is used, but
with the experimental value of Equation 9.73 forg instead of the Dirac value
of 2.
Although the quantum electrodynamic theory of the correction to the g
factor cannot be given here, an attempt can be made to indicate its origin. It
has been stated in Section 9.3 that the Breit interaction between two electrons
is attributable to the emission of a virtual photon by one electron and its sub-
sequent absorption by the other. In the same way an isolated electron can
interact with its own virtual radiation field by emitting a virtual photon, which
it later reabsorbs. In addition, the electron can polarize the surrounding electro-
magnetic field creating a virtual electron-positron pair followed by annihilation
of the pair with emission of a virtual photon which is absorbed by the electron.
(These concepts are not as obscure as they appear, since this description is
analogous to the interaction of a ground state configuration with excited con-
figurations in the electronic theory of molecules, the complications arising
because the radiation field is also involved).
A qualitative picture of how this produces a contribution to the electron’s
spin magnetic moment has been given and is as follows. The spins of the elec-
tron and positron in the virtual pair are generally antiparallel and tend to be
oriented so that one is parallel and one is antiparallel to the spin direction of
the original electron. However, the case where the spin of the virtual electron
is parallel to that of the real electron is preferred; that the two situations are
not equivalent may be seen by noting that annihilation generally takes
place between an electron and a positron with opposite spins and in the pre-
ferred case the virtual positron can annihilate either the real or the virtual
electron, while in the other case only the virtual electron can be involved in
such an annihilation.
The two situations have different magnetic moments, since the electron has
a negative magnetic moment, but the positron has a positive magnetic moment
as a result of its positive charge (Section 8.6). The preferred situation with the
spins of the real and virtual electrons parallel has a negative magnetic moment
with three times the magnitude of an electron alone; the magnetic moment of
the other situation is of the same magnitude as an electron but is positive. If
the two situations were equally probable there would be no correction to the
176 Advanced Molecular Quantum Mechanics

electron’s magnetic moment, but since one is preferred there is a small negative
contribution that accounts for the deviation of the g factor from 2.
When these quantum electrodynamic arguments are expressed quantita-
tively, the correct term is found to be a/7, where a is the familiar fine structure
constant (Equation 8.85). Higher-order corrections have also been calculated,
although a large number of interaction terms have to be considered. One of
the more recent theoretical estimates for the g factor of the electron is:

g = 2+ (a/7) — 0-65696(a/m7)? + 1:49(a/7)? + O((a/m)*). (9.74)

The coefficient of (a/7)’ is well established, but attention has only recently
been directed to the (a/m)* term. Equation 9.74 gives a value for the g factor
that is in good agreement with the experimental value of Equation 9.73.

9.6 The many-electron Hamiltonian

A Hamiltonian for two electrons falls short of our goal of a molecular Hamil-
tonian. Here the extension to a many-electron Hamiltonian is considered; the
inclusion of nuclei is discussed in the next chapter.
The two-electron Hamiltonian (Equation 9.71) may readily be extended
to the case of many electrons provided it may be assumed that there are no
interactions that involve three or more particles. This assumption cannot be
correct, since one electron can influence a second by perturbing the motion of
a third. However, the correction terms necessary may be shown to be of the
order of mc’a®. In addition, the work of Itoh, who used quantum electrody-
namics, confirms that to order mc?a* there are no three-body terms.
In writing the many-electron Hamiltonian the subscripts i andj are used to
distinguish electrons. If the opportunity is taken to introduce the radiative
corrections discussed in the previous section by making the replacement 9.72,
the resultant Hamiltonian is:

KS z [mc? — eg; + 13/2m (a)

+ gup(s;-B;) (b)

Fi (gup/4mc’)s;. [1r; Reais k AT] (c)

+ (eh?/8m?c*)(V.E;) (d)
— (1/8m°c?)
1} — (gug/2m?c?)(s;.B;)7? (e)
+ os {e°/8m €or; ; (f)
The Wave Equation for Many Electrons ‘ATI

— (€7/L6me9m?c) [ri Crijimy) + Oni) (Rij) (g) \(9.75)

— (8 up/8r€9me*r};)s;.(tij ,Ti) (h)
+ (egity/4€ome7r};)s;.(t;; .7;) (i)
+ (g7up /8m€ 9c")[(s;.8;)/r3; — 3(:-tij(ti8/75;
— (817/3)6(4;;)(5;-8;)] (i)
— (e7h?/8e9mc?)5(r;;)} (k)
+ O(mce?a').

Since this Hamiltonian involves a summation over j #i, it has been necessary
to introduce a factor of i into (f), (g) and (j), so that these interactions are not
counted twice.
In Equation 9.73 the subscripts have been dropped from the constants m,
e and g, since the origin of each term may be ascertained by referring back to
Equations 9.37 or 9.71. However, for completeness the identification of each
term is repeated here:
(a) an electron’s rest energy, its energy of interaction with the external
electric potential and its kinetic energy, respectively;
(b) the Zeeman term representing the interaction of an electron’s spin mag-
netic moment with the external magnetic field;
(c) the interaction of an electron’s spin magnetic moment with the magnetic
field it experiences by virtue of its motion relative to the external elec-
tric field;
(d) the Darwin term representing the correction to the second term in (a)
due to an electron’s Zitterbewegung;
(e) relativistic corrections to the kinetic energy in (a) and the Zeeman term
(b);
(f) the Coulomb interaction between pairs of electrons;
(g) the retarded orbit-orbit interaction of one electron with the electromag-
netic field due to the relative motion of another;
(h) the spin-orbit term representing the interaction of the spin magnetic
moment of an electron with its own orbital motion due to the electric
field of another electron;
(i) the spin-other-orbit term representing the interaction of the spin mag-
netic moment of one electron with the orbital motion of another;
(j) the spin-spin term comprising a dipole-dipole interaction between the
spin magnetic moments of two electrons together with a Fermi-contact-
type interaction;
178 Advanced Molecular Quantum Mechanics

(k) a correction to the Coulomb term (f) analogous to the Darwin term (qd).
In the Hamiltonian (Equation 9.75) the mechanical momentum 1; =
(p; + eA;) appears in many terms. It is expedient not to expand these terms,
since this ensures that the Hamiltonian is gauge invariant. However, it should
be noted that when, for example, m;/2m is expanded, an orbital Zeeman term
appears together with a contribution to the diamagnetism (Section 7.1).

Bibliography
The derivation of the two-electron Hamiltonian from the Dirac equation
Carrington, A., Levy, D. H., and Miller, T. A. (1970), ‘Electron resonance of
gaseous diatomic molecules’, Adv. Chem. Phys., 18, 149.
McWeeny, R., and Sutcliffe, B. T. (1969), Methods of Molecular Quantum
Mechanics, Academic Press, New York: Appendix 4.

The Breit interaction

Bethe and Salpeter: pages 170-183.
Rose: pages 225-229.

Reduction of the Breit equation to non-relativistic form

Chraplyvy, Z. V. (1953), ‘Reduction of relativistic two-particle wave equations
to approximate forms. I and II’, Phys. Rev., 91, 388 and 92, 1310: Foldy-
Wouthuysen-type transformations.
Barker, W. A., and Glover, F. N. (1955), ‘Reduction of relativistic two-particle
wave equations to approximate forms. IIP, Phys. Rev., 99, 317: the Foldy-
Wouthuysen-type transformation.
Estabrooks, P. G. (1967), ‘Reduction of the two-electron Breit equation’, WIS-
TCI-264, The University of Wisconsin, Theoretical Chemistry Institute: the
method of small components.

The electron g factor

Wesley, J. C.,and Rich, A. (1971), ‘High-field electron g-2 measurement’, Phys.

Rev. A, 4, 1341: one of the more recent experimental determinations of
the g factor of the electron.
Levine, M.J., and Wright, J. (1971), ‘Sixth-order magnetic moment of the elec-
tron’, Phys. Rev. Letters, 26, 1351: oneof the more recent theoretical evalu-
ations of the g factor of the electron.
Sikolov, A. A., Koskutov, Y. M., and Ternov, I. M. (1966), Quantum Mechanics,
Holt, Rinehart and Winston, New York: a qualitative discussion of the ori-
gin of the g factor correction is given on pages 354-356.

The many-electron Hamiltonian

Itoh, T. (1965), ‘Derivation of non-relativistic Hamiltonian for electrons from
quantum electrodynamics’, Rev. Mod. Phys., 37,159.
Present, R. D. (1971), ‘Non-additive interactions’, Contemp. Phys., 12,595: a
review of the magnitude of three-body interactions.
 CHAPTER TEN

The Molecular Hamiltonian

In extending the many-electron Hamiltonian to a molecule, nuclei must be

introduced. This poses serious problems, since nuclear theory is not in as ad-
vanced a state as electron theory; although simple models exist to explain
nuclear properties, a serious treatment of the topic is beyond the scope of this
book. Fortunately, many of the nuclear contributions to the Hamiltonian are
much smaller than the corresponding electronic contributions and nuclei can
usually be included quite satisfactorily using phenomenological arguments.
Even when a suitable molecular Hamiltonian has been established, its use is
by no means trivial and would require another book to deal with it in depth.
However, there are several excellent texts which essentially start with the
Hamiltonian and treat its application to specific problems in detail. Neverthe-
less the transformation to molecular coordinates and the use of effective
Hamiltonians is outlined briefly here as a general introduction to the problem
of spectral analysis.

10.1 The introduction of nuclei

To obtain a molecular Hamiltonian nuclei must be introduced and to do this

it is necessary to assume that nuclei can be treated as Dirac particles, that is
particles that are described by the Dirac equation and behave in the same
way as electrons. The non-relativistic approximation (Equation 9.75) to the
many-electron Hamiltonian can then be extended to a molecule by pretending
that some of the electrons are nuclei and making appropriate changes in no-
tation. For m, the mass of an electron, we write m,, the mass of nucleus a.
Similarly, s; is replaced by I,, the spin of nucleus a, and Zye is used in place

179.
180 Advanced Molecular Quantum Mechanics

of — e, where Z, is the atomic number of nucleus @.

This procedure involves a number of drastic assumptions, but it has been
shown to be valid provided that only terms involving (nuclear mass)‘ are re-
tained. (The arguments used are quantum electrodynamical and cannot be
given here; the reader is referred to the book of Bethe and Salpeter (pages
193-4) for details.) This means that all terms involving (nuclear mass) *and
smaller are neglected, but in fact all these terms are formally of order mea to
start with and are at least 10° times smaller than the corresponding electron
terms, because the ratio of the proton mass to the electron mass is 1-8631 X
10°.
It might be thought that only the nuclear and electron-nuclear terms in the
Hamiltonian are to be regarded with any suspicion. However, a note of caution
must be sounded about the terms involving just the electrons. It is recalled that
in reducing the Dirac and Breit equations to non-relativistic form, the order of
magnitude of the terms was estimated on the basis of an electron in the first
Bohr orbit of the hydrogen atom. In general higher nuclear charges are involv-
ed and for a one-electron atom in which the nucleus has a charge Ze it is no
longer appropriate to express the magnitude of the terms in the Hamiltonian
as mc’a". Instead the terms c(@.p), e¢ and cea.A in the Dirac Hamiltonian are
of order mc?(Za), mc?(Za)? and mc*(Za)?, so that Za should be used as the
expansion parameter rather than the fine structure constant itself. Since a is
approximately 1/137, these comments only become important for atoms or
molecules involving nuclei with large atomic numbers, and then only for the
inner electrons, since the outer electrons are effectively screened from the
nuclei. It is clear from these remarks that relativistic effects are more impor-
tant if inner electrons and nuclei with large Z are involved. In such cases the
use of an approximate Hamiltonian, which is a power series expansion in Za,
is not satisfactory. One way of avoiding this problem is to take as the zero-
order problem one electron under the influence of a nucleus and then intro-
duce as perturbations the electron-electron interactions including the Coulomb
interactions. The Dirac equation is solved explicitly for a one-electron atom
in the next chapter, but the general problem of nuclei with large atomic num-
bers is too specialized to be considered here.
By assuming that nuclei behave as Dirac particles, it is also assumed that
all nuclei have spin 3, but this is not true. Some nuclei have no spin angular
momentum while nuclear spins as high as 9/2 are not uncommon; in addition,
nuclei with integral spins are bosons and do not obey Fermi-Dirac statistics.
However, if the policy is adopted of assuming that nuclei are Dirac particles, but
that some of them have anomalous spins, the resulting theory is not in disagree-
ment with experiment; again quantum electrodynamics indicates that this is a
valid approach, if only terms involving (nuclear mass)' are retained. A further
The Molecular Hamiltonian 181

complication associated with nuclei which have spins greater than or equal to
1 is that they have quadrupole moments. These are discussed in the next sec-
tion, which is concerned with effects associated with the finite size of the
nucleus; for the present nuclear quadrupole contributions to the Hamiltonian
are merely noted and labelled as Hg.
Associated with a nuclear spin I, is a spin magnetic moment:

Sallnly = 8q(eh/2mp)ly, (10.1)

where fy is the nuclear magneton and differs from the Bohr magneton by in-
volving the mass of the proton m, instead of the electron mass. If nuclei were
true Dirac particles (with, if necessary, anomalous nuclear spins), the spin mag-
netic moment would be:
WZyeh/2my Ny. (10.2)

Even in the case of the proton, where my = m, and Zy = 1, the nuclearg fac-
tor gq is not 2 and as for the electron it is anomalous. However, the anomaly
is much larger than for the electron and the protong factor is in fact 5-5855
even though its spin is .. In this connection we might note that the magnetic
moment of the neutron, which is of the same magnitude as that of the proton,
is completely anomalous, since the neutron is chargeless and would thus be
expected to have no magnetic moment at all. These anomalous magnetic mo-
ments have been explained in terms of the interaction of the proton and neu-
tron with their virtual meson charge clouds, although meson theory is not in
as satisfactory a state as quantum electrodynamics. Larger nuclei also have
anomalous magnetic moments and some are even negative. Finally, we should
note that in practice the ratio (Z./m,) in 10.2 is absorbed into gy, so that
nuclear magnetic moments are given by gyUyIg (Equation 10.1).
We are now in a position to generalize the many-electron Hamiltonian
(Equation 9.75) to a molecule by assuming that nuclei are Dirac particles with
anomalous magnetic moments and spins. In doing this it is helpful to keep in
mind the interpretation of the terms in Equation 9.75 and to consult Equa-
tions 9.37 or 9.71 to see which particle is responsible for quantities such as
mass and charge in an individual term. The molecular Hamiltonian may then
be written as:
Han Soe (10.3)

where H, is the many-electron Hamiltonian (Equation 9.75) and H,, and Hen
are, respectively, the nuclear Hamiltonian and the electron-nuclear interaction
Hamiltonian.
Written explicitly the nuclear Hamiltonian is:
182 Advanced Molecular Quantum Mechanics

0 2 {mc + Zo€by + 14, 2M, — qMn (Ug -Ba)

4 ae ZZ pe?|8M€o%ag} + O(mc?a*(m/mp)’), (10.4)

a

where
TW, = Pa — Zeal Ae: (10.5)

The terms in Equation 10.4 represent, respectively, nuclear rest energy, the
energy of interaction between nuclear charge and the external electric potential,
nuclear kinetic energy, nuclear Zeeman energy and nuclear-nuclear Coulomb
repulsion. The interaction Hamiltonian appears as:

Hen = i os Ze? 14 TE oFie (a)

i,a

au (Z,e7/8megmmyc’) [17;.(ri tte) + (Tia) Tice Fie T)] (b)

— (gUBZ /8ME gC TIq)S;(Kice AT) (c)

a (8 UpZye/4m€9 MgC’ Tin) 8;-(Fic, AT) (d)

+ (gybn €/41€oMC7 iq)

Ney(ice ATi) (e) (10.6)
— (8 qlp bn /47€ C7 )[(S:-An)/Tia — 3(S;-Tia)(To Lied)? io
— (87/3)5 (tia Si-Ly)] Cf)
+ (Zye*h*/8eom*c?)5(Fia)} (g)
+ O(me?a*(m/m,)*) + Ho.
In this Hamiltonian (a) is the electron-nuclear Coulomb attraction term, while
(b) is a retarded orbit-orbit interaction. The electric field due to the nucleus is
responsible for the spin-orbit interaction term (c). Both (d) and (e) are spin-
other-orbit interactions involving the spin magnetic moment of an electron
and the motion of a nucleus and vice versa. The term (f) represents the inter-
action between the spin magnetic moments of an electron and a nucleus; in
addition to the dipole-dipole interaction, which has a classical analogue, there
is a term involving a Dirac delta function, which represents the Fermi contact
interaction and has no classical analogue. Finally, there isa Darwin-type term
(g) and the nuclear quadrupole interaction term Hg.
No terms involving (nuclear mass)” have been included in Equations 10.4
or 10.6, since their presence cannot be rigorously justified, but this does not
mean that there are no significant terms of this type. Indeed the dipole-dipole
interaction between two nuclear spin magnetic moments, that is observed in
broad line nuclear magnetic resonance experiments, is of this type and so is
The Molecular Hamiltonian 183

the interaction between molecular rotation and nuclear spin magnetic mo-
ments, that is seen in molecular beam studies. Terms like this have analogues
in the two-electron Hamiltonian and are quite plausible, but their inclusion
must be based on phenomenological arguments.

10.2 Finite nuclear size effects

In this section two additional nuclear effects are mentioned, which may be
attributed to the fact that nuclei are not point charges but have finite extent;
of course, both the angular momentum and the magnetic moment associated
with nuclear spin might also be attributable to this.
Apparently electrons can penetrate nuclei and move about inside them. In
atoms only s electrons have a finite probability of being at the nucleus, and
when such electrons are inside the nucleus the electric potential they experi-
ence is not given by Ze/47€or, but is presumably less than this. Consequently the
energy of an s electron is shifted upwards because of the finite size of the
nucleus, but the magnitude of this effect is dependent on the structure of the
nucleus involved. In particular, different isotopes of the same element have
different shifts, since the nuclei are different; isotope shifts have been detected
experimentally, but the effect is small and has only been observed in the spec-
tra of heavy atoms (Z > 50). A more important consequence of this effect is
in Mossbauer spectroscopy, where the observed transitions are between differ-
ent nuclear energy levels. Since the size of a nucleus alters during these tran-
sitions, the exact energy change involved depends on the environment of the
nuclei and in particular the distribution of the electrons in the molecule. These
effects must be treated phenomenologically in view of the uncertainty about
nuclear structure.
The other consequence of finite nuclear size is that many nuclei have quad-
rupole moments. One model that is frequently given takes the nucleus to be a
collection of (charged) protons and (uncharged) neutrons. If the position of
proton p in nucleus a relative to the centre of charge of nucleus @ is rpq,
the electrostatic interaction energy between the nucleus and an electron at
position feq is:
eo. = 2 € [Amegitan'= thal. (10.7)

Normally the electron is well outside the nucleus so that Equation 10.7 may
be expanded as a power Series in fpq about req. This may be accomplished by
noting that:
f(r—a) = [1—(a.V) + xa.V) +... 1f@). (10.8)
184 Advanced Molecular Quantum Mechanics

Use of Equations 2.78 and 2.96 then gives:

Ulta —trols, Uleack Geoitey) taee helen am BUT gels) clea eee
(10.9)

a term involving 5(teq) has been omitted, since it is assumed that rea> rp
When Equation 10.9 is substituted into Equation 10.7 the first term that
arises is — D e7/41€oreg = —Zge’/4m€oreg, Which is the familiar Coulomb
Dp
term. The next contribution involves 2 ery,, which is the electric dipole
D
moment of nucleus a, and vanishes, since rpq is the position of a proton
relative to the centre of charge of the nucleus. Although the model used here
is a simple one, it is a general result, both experimentally and theoretically,
that nuclei have no electric dipole moments. The theoretical demonstration of
this fact is based on the assumption that the states of nuclei have definite
parity, that is they are either symmetric or antisymmetric with respect to the
inversion of all coordinates. The expectation value of the electric dipole
moment operator, which is of odd parity, must then vanish.
The third and fourth terms in Equation 10.9 are both quadratic in the com-
ponents of rpq and may also be factorized into the product of an electronic
term and a term dependent on nuclear structure:

rat Teel ot se ul 3 (rey tay) /2S Grveat par Sieh a OrcetaairoRlea Orca

(10.10)

as may easily be verified; the additional subscripts, 7 and k, distinguish vec-

tor components and, since the repeated subscript summation convention is in
operation, 5;,5;, = 3 (Equation 2.21). The contribution of these terms to
Equation 10.7 is thus a scalar product of two second-rank tensors:

(1/6)OSP VP, (10.11)

where
Of =e = (rp jFrak = SinT
oa) (10.12)
is a component of the nuclear quadrupole tensor of nucleus a; it has even
parity so that its expectation value is non-zero and, since it depends on nuclear
structure, it is treated phenomenologically, although its matrix elements do
depend on the nuclear spin I,. The other tensor has components:
V unre (e/47€ oreo )(3reajFeak aa Gielen): (10.13)
and is known as the electric field gradient tensor, since its components may
also be written in the form:
V SS = ViVi
(— €/42€ req), (10.14)
The Molecular Hamiltonian 185

provided the electron is always taken to be outside the nucleus so that the
delta function contained in the right-hand side of Equation 10.14 may be ig-
nored. Equation 10.13 may be extended by summing over all the electrons in
the molecule and, with a little modification, the contribution of other nuclei
may be included. The total nuclear quadrupole interaction energy Hg is then
given by a summation of the expression 10.11 over all’ the nuclei in the
molecule.
The largest of the terms that have been neglected in the expansion (Equa-
tion 10.9) are cubic in the components of rpq and are related to the electric
octupole moment of the nucleus. However, they vanish, since parity arguments
show that nuclei do not have electric octupole moments. Thus the next non-
zero contribution to Equation 10.7 involves the electric hexadecapole moment
of the nucleus, but at present this is of no experimental significance. In this
connection we might note that, of the nuclear magnetic moments, the mono-
pole and quadrupole moments are zero, but that the dipole and octupole mo-
ments do not vanish; the dipole moment has already been considered, but, al-
though magnetic octupole moment effects have been detected in iodine, indium
and gallium atoms, they are at present at the limit of experimental significance.

10.3. Spectroscopically useful Hamiltonians

The molecular Hamiltonian that has been derived here is expressed in terms of
the position vectors of the individual particles. This form has the disadvantage
that it does not reflect the basic physical features of molecules. A molecule is
essentially a semi-rigid nuclear framework supporting a distribution of elec-
trons which is responsible for the chemical bonds. (In this and the following
section molecules are considered, but atoms can always be regarded as special
cases.) Because nuclei are much more massive than electrons, nuclear and elec-
tronic motion are largely separated from each other and have very different
energies; in addition, molecular translation, rotation and vibration also have
characteristically different energies from each other. Consequently, it is ex-
pedient to write the Hamiltonian of a molecule in such a way that translation,
rotation, vibration and electronic motion are separated as much as possible.
To do this it is appropriate to change the molecular variables from the position
vectors of individual particles to translational, rotational, vibrational and elec-
tronic coordinates.
Since the Hamiltonian includes relativistic corrections, it might be thought
that a Lorentz transformation should be used in transforming to molecular
coordinates. However, the frame of reference in which physical measurements
are made is not changed so that the transformation is merely a change of
186 Advanced Molecular Quantum Mechanics

variables within a particular inertial frame.

The transformation may be thought of as taking place in three stages. First,
translation is separated by changing the origin of the coordinates from a space-
fixed one to the molecular centre of mass keeping the axes parallel to the
original space-fixed axes. Without moving the origin, but changing to axes ro-
tating with the molecule, rotation may be separated off. Finally, the electronic
motion may be separated most effectively from the vibrations by shifting the
origin of the coordinates to the centre of mass of the nuclei without altering
the orientation of the axes.
The transformation of the approximate field-free Hamiltonian:

KH = D p2/2my,+ = p?/2m + V, (10.15)

Qa t

where the potential energy V comprises the Coulomb interactions, is perform-

ed in anumber of texts with the result that:

H = P?/2M+3N.y.N+ 5D P2+ > p?/2m + (Dp,)*/2Myt V, (10.16)

If Uy L

where p; is now the momentum of electron / in the molecule, that is it is the

momentum conjugate to the position r; of electron? relative to the new origin
at the centre of mass of the nuclei. Other new quantities in Equation 10.16
are the total mass of the molecule M (= 2 m, + 2 m) and the mass of the
a l

nuclei alone My (= 2 m,). The translational momentum P is the momentum

a

conjugate to R, the position of the centre of mass of the molecule; in terms

of the original space-fixed coordinates this is given by R = (2 mgtq + Z mr;)/M.
a l

The position ry, of a nucleus in the molecule may be expressed in terms of

normal coordinates Q,:
fy = 1+ E me larOr, (10.17)
wile

where rQ is the equilibrium position of nucleus a and the 1,, are constant vec-
tors chosen so that the normal coordinates are orthogonal to each other and
to the molecular rotations and translations; the P, are then the vibrational
momenta conjugate to the vibrational coordinates Q,. The vector N is the
rotational angular momentum of the nuclei and differs from the total angu-
lar momentum J of the molecule by the electronic and vibrational angular
momenta, L and G respectively:

N= JL G = Fearn 2 tare (10.18)

where the components of §,, are the so-called Coriolis coupling constants:

Cs = Z hor alas- (10.19)

a
The Molecular Hamiltonian 187

Finally, u is the inverse of the instantaneous inertia tensor I, the elements of

which are given by:
Ly = Cem ej ~ MoFarlar— & Crs)i(Ges)iQrOe- (10.20)
The main problem associated with the derivation of Equation 10.16 is that
the rotational momentum N is not conjugate to any coordinates. However,
the components of the total angular momentum J are conjugate to angles de-
fining the orientation of the molecule. Even so Equation 10.16 is not at all
easy to derive and it is usual to perform the transformation in a round about
way rather than directly. First, it is easier to transform classical expressions
rather than quantum mechanical expressions; after the transformation it is
necessary to write the resulting classical Hamiltonian in a quantum mechanical
form and this involves choosing the correct order for operators, but techniques
exist for doing this. Another simplification is to use the classical Lagrangian
instead of the corresponding Hamiltonian, since the Lagrangian is a function
of velocities, which are easier to transform than the momenta used in the
Hamiltonian; the transitions from velocities to momenta and Lagrangians to
Hamiltonians may be performed using the relations to be found in Chapter 3.
Finally, we should note that difficulties are encountered in considering linear
molecules, which have no nuclear moment of inertia about the molecular axis
in the equilibrium position. Consequently, it is not possible to invert the inertia
tensor I to get u, but this difficulty can also be circumvented.
Of course the Hamiltonian that we have derived is much more complicated
than Equation 10.15, since it includes relativistic corrections and external
electromagnetic fields. Nevertheless, the full Hamiltonian has been transformed
to molecular coordinates. The main feature of the result is that, after negligible
terms have been omitted, the leading terms in the transformed Hamiltonian
are similar to Equation 10.16 and the correction terms, which were omitted
from the approximate Hamiltonian (Equation 10.15), are essentially unchanged
in form by the transformation except that they are expressed in terms of
molecular coordinates. This is particularly true of the electronic terms, although
some so-called mass polarization correction terms appear because the positions
of the electrons are now measured relative to a molecule-fixed rather than a
space-fixed origin. However, the parts of the Hamiltonian involving nuclear
momentum have to be reinterpreted in terms of molecular rotation and vibra-
tion. For example, the spin-other-orbit interactions 10.6d between the spin
magnetic moments of the electrons and the motion of the nuclei leads to spin-
vibration and spin-rotation interaction terms.
Any further discussion of this topic would take us outside the scope of this
book and reference must be made to the sources given in the bibliography at
the end of the chapter.
188 Advanced Molecular Quantum Mechanics

10.4 Effective Hamiltonians

To use the molecular Hamiltonian it is necessary to solve the corresponding

Schrodinger equation to obtain the eigenvalues and eigenvectors of the mole-
cule under consideration. Exact analytic or numerical solution of the appro-
priate Schrodinger equation is of course impossible, but even if it were possible
such an approach would not be rigorously justifiable. This is because the
Hamiltonian itself is based on the Breit equation, which is only correct to
order mc’a’. In addition, the Breit operator is obtained using perturbation
theory, so that operators derived from it (those based on the terms appearing
in Equation 9.70) should only be used in first order. This means that only an
approximate solution of the Schrodinger equation is necessary and the use of
perturbation theory is quite in order.
The usual approach is to choose a set of basis functions (approximate
eigenfunctions of the Hamiltonian), construct the Hamiltonian matrix and
diagonalize it. However, a complete set of basis functions would be infinite
and some method of simplification or approximation is necessary. For many
problems the majority of the terms in our Hamiltonian are too small to be
significant and may be omitted, but the influence of these terms may be de-
tected by a number of high resolution techniques such as magnetic resonance
or microwave spectroscopy. The information obtained from these high resol-
ution experiments is not in general concerned with the energy separation
between vibronic (vibrational-electronic) states, but with the rotational and
spin energy levels associated with a particular vibronic state.
For the Hamiltonian expressed in molecular coordinates it is appropriate
to use a separable representation with the basis functions of the form:

(i Weranel soty vib alV elena auesos (10.21)

where W trans is a translational wave function and depends only on the position
R of the centre of mass of the molecule, W,,; is a rotational wave function
depending on the angles specifying the orientation of the molecule, Wy, is a
function of the (vibrational) normal coordinates Q, and the electronic wave
function W., depends only on the electronic coordinates r; (and possibly on
Q, as well); Weisp and Wnuesp are electron and nuclear spin functions, respec-
tively. The translational part of the problem may easily be separated off,
since at present there appear to be no significant interactions between trans-
lation and other types of molecular motion. However, there are important
interactions between electronic, vibrational and rotational motion and, in ad-
dition, external electromagnetic fields may be present.
In principle the molecular Schrodinger equation could now be solved by
setting up the Hamiltonian matrix and using appropriate techniques to
The Molecular Hamiltonian 189

diagonalize it with sufficient accuracy. However, the state of electronic theory

is such that suitable electronic basis functions for a molecule are difficult to
obtain and their energies are not known very accurately; this is particularly
true for the excited electronic states. The same is true to a lesser extent for the
vibrational functions, which depend on a knowledge of the vibrational poten-
tial function. Consequently, this approach is not suitable for the interpretation
of high resolution spectra involving the rotational and spin fine structure ofa
specific vibronic state.
What is needed is an effective Hamiltonian that is only appropriate to the
vibronic state under consideration. Only spin and rotational operators (and
perhaps electronic and vibrational angular momentum operators) appear in
such a Hamiltonian together with a number of parameters specific to the vi-
bronic state. These parameters are averages of electronic and vibrational opera-
tors over the vibronic state and in addition contain contributions to allow for
the mixing of vibronic states by coupling terms in the Hamiltonian. The numeri-
cal values of these parameters are such that the eigenvalues of the effective
Hamiltonian are exactly the same as those that would be obtained for the par-
ticular vibronic state using complete diagonalization of the Hamiltonian, if that
were possible. Thus an effective Hamiltonian imitates the complete Hamil-
tonian so far as one particular vibronic state is concerned.
The advantage of effective Hamiltonians is that it is easy to choose the
basis functions to be used for their diagonalization and, in particular, the rigid
rotor wave functions may be used for the rotational wave functions. Of course
there are an infinite number of rotational basis functions and in general the
effective Hamiltonian matrix does not factorize but, since interest usually
centres on the lower rotational levels of a vibronic state, this Hamil-
tonian matrix may usually be truncated at a fairly low rotational level without
loss of accuracy. In addition, the matrix elements of the operators are well
known.
Estimates of the parameters in an effective Hamiltonian may be obtained
in two ways. First, analysis of a spectrum using the effective Hamiltonian gives
an experimental determination of their values. Secondly, although diagonaliz-
ation of the complete Hamiltonian is not possible, the parameters may also be
estimated theoretically from vibronic wave functions by using perturbation
theory. In addition to first-order contributions from the vibronic state under
consideration, there are second- and higher-order contributions arising from
the mixing of vibronic states. This calculation of the parameters depends
largely on the quality of the electronic wave functions used, so that com-
parison with the experimental values provides a test of the electronic wave
functions.
190 Advanced Molecular Quantum Mechanics

To illustrate these statements, we consider the simple example of a rotating

closed-shell spherical-top molecule in its ground electronic state. If vibrations
(and translations) are neglected, the approximate Hamiltonian (Equation
10.16) may be written as:
H = HatHrot = He + ZBN’, (10.22)
where J, is a purely electronic Hamiltonian. For a molecule with spherical
symmetry the rotational kinetic energy can be written in terms of one inertial
parameter B and, since vibrations are neglected,B is a function of the masses
and the equilibrium positions of the nuclei only and commutes with the nu-
clear rotational angular momentum operator N, which differs from the total
angular momentum J by the electronic angular momentum L:
N = J-L. (10.23)
The eigenvectors and eigenvalues of the electronic Hamiltonian # are
taken to be w,, and E,, so that:

Han = EnWn- (10.24)

In this notation the ground electronic state is Wo and it is further assumed
that this is non-degenerate so that the expectation value of L over Wo vanishes.
However, the perturbation #,.; introduces some electronic orbital angular
momentum by mixing Wo with excited electronic states. This may be seen by
expanding H,,; using Equation 10.23:
Hrot = 3BU° —BJ.L + 3BL’. (10.25)
The third term is diagonal in the electronic state and may conveniently be
absorbed in #, but the second term has matrix elements between different
electronic states. The effect of this term may be accounted for by using first-
order perturbation theory to obtain an improved wave function Wo for the
ground electronic state:

Wo Yo a eg Ynl—-BILIYO) Yn WE, = Bo)

Vot BU; E WnlLilVorlWn)(En—Eo). (10.26)

The expectation value of a component L ; of the orbital angular momentum in
the ground electronic state is then given to first order by:

(Lj) = (ho ILjlv)

ee 2BJ; eo Volky Wn Xn lLilWo/En — Eo). (10.27)

This expression for (ZL;) still contains the operator J;, but the introduction of
orbital angular momentum into the ground state is due to molecular rotation
The Molecular Hamiltonian 19]

and Equation 10.27 still has to be averaged over the rotational states.
The total Hamiltonian is from Equations 10.22 and 10.25:

H = H+ 3B? —BI.L, (10.28)

where the third term in Equation 10.25 has been absorbed in H. This may
be changed into an effective Hamiltonian operating only within the electronic
ground state, if the operator L in Equation 10.28 is replaced by its expectation
value in that state. Thus substitution of Equation 10.27 gives the effective
Hamiltonian:

H = Eot BP — B,J; &WolLilWnWnlLjlo/(En — Eo). (10.29)

When it is recalled that the molecule under consideration has spherical sym-
metry, Equation 10.29 can be simplified further:

H = Eot+ 3B's’, (10.30)

where B’ is:
Rear Fe yolks lw, ?/E,, — Eo). (10.31)

Thus to consider the rotational levels of the ground electronic state it is

only necessary to use an effective Hamiltonian (Equation 10.30) operating
entirely within this state. The influence of the excited electronic states is ac-
counted for by the use of an effective rotational constant B’, which differs
from B, the rotational constant of the nuclei alone, by a term that can be
interpreted as the contribution of the electrons to the molecular rotational
constant.
Another example of the use of effective Hamiltonians concerns the g fac-
tors of free radicals. Experimental measurements show that for radicals, which
contain one unpaired electron and which are in electronic states devoid of
electronic orbital angular momentum, the g factors often differ significantly
from the free electron value. This occurs because spin-orbit coupling can mix
electronic states and consequently introduce some orbital angular momentum
into the state under consideration. This may be allowed for by using an (effec-
tive) spin Hamiltonian in which the unpaired electron g factor is permitted to
differ from the free electron value. The magnitude of the discrepancy then
gives information about the way in which spin-orbit coupling operates in the
particular molecule.
These are simple examples and in general the situation is more complicated.
Depending on the problem under consideration there can be many small terms
in the Hamiltonian that are responsible for significant mixing of vibronic states.
In addition, second-order perturbation theory is often not accurate enough
192 Advanced Molecular Quantum Mechanics

and higher-order perturbations must be included. This can be rather compli-

cated, but the procedure may be simplified by using so-called degenerate
perturbation theory; until recently the technique of degenerate perturbation
theory suffered from the disadvantage that high-order terms were not
Hermitian, but this fault has now been remedied.
At present, the reduction of the molecular Hamiltonian to an effective
Hamiltonian operating within a single vibronic state has not been given for a
general molecule. Indeed such a reduction would probably be much too com-
plicated to be of any practical use. Instead each new problem has to be treated
on its merits, but it must be emphasized that great care must be taken to ensure
that all possible contributions to a parameter in the effective Hamiltonian have
been considered. This is particularly important if experimental and calculated
values of the parameter are being compared as a test of the quality of an
electronic wave function.
It is not the purpose of this book to go into the details of spectral analysis,
so again the reader is referred to the bibliography for further information.

Bibliography

The introduction of nuclei

Bethe and Salpeter: the justification for treating nuclei as Dirac particles with
anomalous spins and magnetic moments is given on pages 193-194.
Ramsey, N. F. (1953), Nuclear Moments, Wiley, New York.
Shore, B. W., and Menzel, D. H. (1968), Principles of Atomic Spectra, Wiley,
New York: nuclear effects are discussed on pages 313-319.

Spectroscopically useful Hamiltonians

Howard, B.J.,and Moss, R. E. (1970), ‘The molecular Hamiltonian I. Nonlinear
molecules’, Molec. Phys., 19, 433: the transformation of the Hamiltonian
(Equation 10.3) from space-fixed to molecule-fixed coordinates.
Howard, B. J., and Moss, R. E. (1971), ‘The molecular Hamiltonian II. Linear
molecules’, Molec. Phys., 20, 147: the transformation to molecular coordi-
nates for linear molecules, which present special problems.
Wilson, E., Bright, Jr., Decius, J. C., and Cross, P. C. (1955), Molecular Vibra-
tions, McGraw-Hill, New York: Chapter 11 describes the transformation to
molecular coordinates for a nuclear Hamiltonian.

Degenerate perturbation theory

Bloch, C. (1958), ‘Sur la théorie des perturbations des états li¢s’, Nucl. Phys.,
6, 329.
Messiah, A.(1961), Quantum Mechanics, North-Holland, Amsterdam: pages
712-720.
The Molecular Hamiltonian 193

Pryce, M. H. L. (1950), ‘A modified perturbation procedure for a problem in

paramagnetism’, Proc. Phys. Soc. A, 63, 25.
Soliverez, C. E. (1969), ‘An effective Hamiltonian and time-independent per-
turbation theory’, J. Phys. C., 2, 2161: the effective Hamiltonian derived
here is Hermitian to all orders.

Examples of effective Hamiltonians and their use

Brown, J. M. (1972), ‘Electron resonance of gaseous free radicals’, MTP Inter-
national Reviews of Physical Chemistry (Series 1), 4,235.
Carrington, A., Levy, D. H., and Miller, T. A. (1970), ‘Electron resonance of
gaseous diatomic molecules’, Ady. Chem. Phys., 18, 149.
Carrington, A., and McLachlan, A. D. (1967), Introduction to Magnetic Reso-
nance, Harper and Row, New York: spin Hamiltonians are discussed in
Chapter 9.
Eshbach, J. R., and Strandberg, M. W.P.(1952), ‘Rotational magnetic moments
of 'Y molecules’, Phys. Rev., 85, 24.
Van Vleck, J. H. (1951), ‘The coupling of angular momentum vectors in mole-
cules’, Rev. Mod. Phys., 23, 213: Appendix 1.
CHAPTER ELEVEN

The Hydrogen Atom

In non-relativistic theory the hydrogen atom is one of the few cases for which
the Schrodinger equation may be solved exactly. For this to be possible the
proton and electron are assumed to be spinless, and the only role that the pro-
ton plays is to provide an attractive Coulombic potential; the finite mass of
the proton may, of course, be taken into account by using a reduced mass
for the electron.
If the proton is regarded as merely an infinitely massive source of electro-
static potential, the Dirac equation for the electron may also be solved exactly.
This chapterisdevoted to its solution using this model for a one-electron atom,
although the more general case where the nucleus has charge Ze is considered,
since the results demonstrate that relativistic effects are increasingly im-
portant for heavy atoms. It is noted that the effect of the finite mass of the
nucleus could be largely accounted for by using a reduced mass for the elec-
tron, although unlike the non-relativistic case this procedure is not exact. Even
with the simplification of an infinite mass for the nucleus, the mathematics
involved is tedious though straightforward and for this reason only an outline
will be given. However, the reader should by now have acquired some facility
inthe manipulations involved in evaluating commutators, for example, and no
difficulties should be encountered.

11.1. Non-relativistic theory for a one-electron atom

The solutions of the non-relativistic Schrodinger equation for a one-electron

atom are summarized here, since they provide a starting point for the solution
of the relativistic problem and a number of their properties will be used later.

194
The Hydrogen Atom 195

In addition, this brief review facilitates comparison of the relativistic and non-
relativistic solutions.
The non-relativistic Hamiltonian is:

Ho = p?/2m— Ze?/4neor, (11.1)

where r is the position of the electron relative to the nucleus and the second
term represents the potential energy of the electron in the electric field of the
nucleus. This Hamiltonian commutes with the components of the orbital
angular momentum operator fil (= r , p), so that Ho, 7 and 1, are separately
constants of motion with the eigenvalues Eo, /(/ +1) and m,, respectively.
If the quantum number 7 (= 1, 2, . . .) is introduced the eigenvalues of the
Hamiltonian are:

Ey = —me2
8h egn = — mZ0 nn’, (it 2)
where a (= e*/2heoc) is the fine structure constant (Equation 8.85). Using
spherical polar coordinates (7, 6, ¢) for the position of the electron relative to
the nucleus the corresponding eigenfunctions may be written as the product
of radial and angular parts:

Vnlm, = Ryilr) Yim O, 9); (11.3)

for a given value of n the quantum number / is restricted to the values

0,1,...,(2—1), while m, can only take the values /,(/—1),...,—J/. All
solutions with the same value of ” have the same energy, so that the energy
levels exhibit a degeneracy of n’.
The radial functions R,,,(7) may be expressed as:
3
Rul?) = (22 ou exp (— pln)(2p/n)'L2} p/n), (11.4)
where

LS Qen) = AG 1)°*'[(n + D!PQp/ny’/(n—1—1—k)(214+ 144K!

(11.5)

is an associated Laguerre polynomial, p is a dimensionless quantity:

p = Zrlao (11.6)

and do (= 4m€oh"/me?) is the Bohr radius. In general these radial functions ex-
hibit nodes, that is they vanish for certain values of r; in particular, the func-
tion R,,,(r) has (n — /— 1) nodes.
196 Advanced Molecular Quantum Mechanics

The angular functions Y;,,(0, 6) are of more interest, since they will be
used to construct the solutions of the Dirac equation. Specifically they are
spherical harmonics and may be written as:

Yim (0,0) = [(21+ 1) — m)!/4m( + m)!]? Pim (cos 0) exp (im), (11.7)
where
ie l+m l+m

Pim (cos 0) = Galas? “(sin 0)" magenta!

— 11.8
27 Geos oer oy aL)
is an associated Legendre polynomial. These angular functions also have nodes,
the number being given by the quantum number /. However, the important
thing to note is that they are eigenfunctions of the operators I? and L,:

i ee oy d+ 1) Yim; L.Yim, = MY im) (11.9)

In addition, their behaviour under the operators /,. and l, may be expressed in
the following manner:

LYimy = (le + ily Yim, = (@— m+ my + DIY, myers ae

1Viney =e thy Vimy = AE Hm) rt PY, opt
The probability density of the electron in an atomic orbital is given by the
square of the wave function (Equation 11.3). Since the radial and angular
parts of the wave function have (n —/— 1) and / nodes, respectively, the prob-
ability density exhibits (x — 1) nodes. This fact raises the problem of how an
electron in an atomic orbital crosses these nodes. This question can be dis-
missed as being improper, since the uncertainty principle does not permit an
electron to be located at a node anyway. Alternatively, a node may be regarded
as being a mathematical concept of no physical significance. However, it will
be seen later that in relativistic theory the electron probability densities are in
fact nodeless.
This section is concluded by noting certain expectation values, which will
be of use later. For an electron in an atomic orbital represented by the wave
function Ynim, the expectation values for the operators r-',r-?, r-3 and 8(r)
are given by:

Va = Lian: (r?) = Z?/abn3(1+ 5);

cI ka
(3) = Z3/agn3l(l+ 3) + 1); (8(r)) = 8)9Z */agnPr;
for an s orbital (= 0) the expectation value of 77? is infinite and this fact
causes difficulties in the next section. In addition, the expectation value of p*
may be determined by first using Equations 11.1 and 11.2 to show that:
The Hydrogen Atom |
oag!

Pp? = — mc?a?(Z?[n? — 2Zap/r). (1642)

Thus:
(p*) ll= mic*a* [Z4/n* — 4Z 349 (r7!)|[n? + 4Z a2 (r -2)]

= (m*c*Z*a4/n?) [— 3/n + 4/(1+ 5), (11.13)

where Equations 11.11 have been used.

11.2 The non-relativistic approximation of the Dirac equation

In Chapter 8 the non-relativistic approximation to the Dirac equation was

developed. The approximate Hamiltonian may be written as:

H = me? +Hot+ H, + O(mc’a'), (11.14)

where 4 is given by Equation 11.1 and H, is to be regarded asa perturbation.
The explicit form of 4, may be obtained by substituting the appropriate
electromagnetic potentials into Equation 8.142. For a one-electron atom the
electric potential experienced by the electron is Ze/47€
or, but the vector poten-
tial vanishes. Consequently, the electric field at the electron is Zer/4m€gr°,
while the magnetic field is zero. It is easy to show that the divergence of the
electric field is:
V.E = Ze8(r)/€ (11.15)
and that:
p,E—E,p = —2E,p = — Zehl/2n€ or’), (11.16)

where fil is the orbital angular momentum operator. Thus:

Hy, = —p*/8mec? + (Ze*h*/8neom?c’) [r-7s.1 + 75(r)]

= — p4/8mc? + smc?Za‘a3 [r-35.1 + 75(r)], (11.17)
a result which may be confirmed by referring to the approximate Hamiltonian
(Equation 9.71) for two electrons and allowing the momentum and spin of
one of the electrons to vanish; the three terms in Equation 11.17 are, respec-
tively, a relativistic correction to the kinetic energy, a spin-orbit coupling term
and a Darwin-type correction term.
The perturbation H, contains the spin-operator s, so that the basis func-
tions (Equation 11.3) are not satisfactory as they stand. Since the components
of s commute with Ho, this may be remedied by multiplying each of the orbital
basis functions by a two-component spin function characterized by the spin
quantum numbers s (= x) and m, (=+ +). Such a spin function is an eigen-
function of the operators s* and s, with eigenvalues s(s + 1) (= 3/4) and mg,
198 Advanced Molecular Quantum Mechanics

respectively, and the behaviour of the functions under the operators s, and
sy is given by equations analogous to Equations 11.10 for the corresponding
orbital angular momentum operators. However, perturbation theory using
these new basis functions cannot be used directly, since the operator s.l in H,
(Equation 11.17) has non-zero off-diagonal matrix elements between levels
which are degenerate in zeroth order; the other operators in d(; only connect
levels with different 1. This problem may be overcome by choosing new basis
functions, which are linear combinations of the old, but which are diagonal in
the operator s.l. One way of doing this is to diagonalize the matrix of s.l for a
given value of n, but a different approach is used here.
The root of the problem is that the basis functions are characterized by the
quantum numbers m, and m,, but that the perturbation H, does not commute
with the components of the operators l and s. On the other hand /” and s* do
commute with #,, so that / and s are still good quantum numbers. However,
the components of the total angular momentum operator:

j = I+s = 1+ $e, (11.18)

also commute with JC, as one might expect from the results of Section 8.4.
Thus, instead of using simultaneous eigenfunctions of /7, s”, , and s, as a basis,
a new set of commuting operators may be used to construct new basis func-
tions; explicitly these operators may be chosen to be j”, 1”, s* and j,, which
have the eigenvalues j(j + 1), 1(/+ 1), s(s + 1) and m;. The way in which the
two sets of basis functions are related and in particular the identity of the new
set need not concern us yet and is considered in detail in the next section. The
advantage of the new set is that they must also be eigenfunctions of the oper-
ator s.l with eigenvalues 3 VU + 1) — 1+ 1) — s(s + 1)], since from Equation
$1 18:
sl = i(j?—
I?—5?); (11.19)
this relationship also shows that s.l commutes with j?, /?, s? and KH.
Of course, the new quantum numbers j and m; are restricted. For a given
value of 7 the quantum number m; can only adopt one of the (2j + 1) values /,
(j—1),...,—j. More importantly, reference to Equation 11.18 shows that,
since s = , the values of the quantum number j can only be (/ + 7) Ortr—= *)
for a given value of /. In addition, since j is related to the eigenvalue of the
operator j”, it must be positive, so that for /=0 the only value that j can take
ist s, the value — x not being allowed.
The specific value of 7 for a given value of / indicates whether the electron
spin is oriented parallel or antiparallel to the total angular momentum. Another
way of distinguishing these possibilities is to quote the eigenvalue of the
The Hydrogen Atom 199

operator s.l or the related operator:

Resor 1 = 25.
4~1. (11.20)
whose eigenvalues are given the symbol k. This new quantum number conveys
no new information, but may be used instead of / or j. The reason for its
introduction here is that its use facilitates the solution of the Dirac equation
later in this chapter.
The restrictions on the values of k may easily be determined. From the defi-
nition of the operator K (Equation 11.20):
K?
1 + 2(0.1) + (@.1)?
ll 1+2@1)+2 +ic.d,b

L+ol)+?, (11.21)
where use has been made of the relation 8.40 and the fact that 1,1 is just il.
Substitution for (¢.I) using Equation 11.20 now gives the operator equation:

= KA—Ky (1:22)
so that:
Aha 1) = K(k 1); (11.23)

A relationship between j and k may be obtained from Equation 11.19 by sub-

stituting for s.l (Equation 11.20), /? (Equation 11.22) and s* (= 3/4). The
resulting operator equation:
j? = K*- 3 (11.24)
shows that:
iG +1) = (k +k —3). (11.25)
Solution of the Equations 11.23 and 11.25, together with a knowledge of the
allowed values of j and / gives the following possible combinations of quantum
numbers; if k is positive:

ee psa he eae er oust ie (11064)

while for negative k:

fa — kf = i = ka kk S12... 1). 011,26b)

Thus, the sign of k indicates whether the electron spin is parallel or anti-
parallel to the total angular momentum; k cannot be zero, since j and / must
both be positive. Again it is noted that k is an additional quantum number
that gives no extra information but leads to simplifications later.
The new set of basis functions, characterized by the quantum numbers /, /,
200 Advanced Molecular Quantum Mechanics

s (= }), k and m,, can now be used straightforwardly in a first-order perturba-

tion treatment, since H ; now has no matrix elements between degenerate basis
functions. The contribution from the first term in the perturbation (Equation
11.17) is, from Equation 11.13:

—(p4)/8m3c? = (mc?Z4a4/2n3)
[3/4n — 1/(1+ 5)], (11.27)
while the spin-orbit coupling term gives:

ime? Zotagir 3s.) = me?Z4a* [ij + 1)—1(1+ 1) —s(s + 1] /4nFl+ 5) +1),

(11.28)

where Equations 11.11 and 11.19 have been used. For /= 0 the expression
11.28 is strictly indeterminate, since 7=s= 5 and both the denominator and
numerator vanish. However, agreement with experiment is obtained if it is
taken to be zero, a choice which is confirmed by the exact solution of the
Dirac equation. Finally, the Darwin-type term makes a contribution:

smc’Zatagn (5(r)) = me?Z*a*5),/2n°, (11.29)

where again Equations 11.11 have been used. Although the spin-orbit term
vanishes for /= 0, this is compensated by the Darwin-type term, which only
contributes when /is zero.
To obtain the total first-order correction to the energy provided by the
perturbation # , the last three equations must be added. In doing this, use may
be made of the facts that s = } and that jcan only take the values (/ + $) and
(Gs +). The result for both these possibilities is given by the same expression:

— (me?Z*o4/2n°)[1/(7 + $) — 3/47]. (11.30)

For a given value of n the maximum value of j is (n — 4) so that 11.30 is
negative and the inclusion of relativistic corrections always leads to a lowering
of the energy.
The eigenvalues of the approximate Hamiltonian (Equation 11.14) are thus:

E = me?{1— 2707/2n? — (Z4a4/2n°)[1/(j + 3) — 3/4n] + O(Z 0°) }.

nm

(11.31)
In the non-relativistic theory all levels with the same value of n are degenerate,
but this degeneracy is lifted when the relativistic corrections are included.
However, for a given n the energy of a level only depends on the quantum
number j and not on 1. If only the spin-orbit coupling had been included, the
energy would have been a function of / as well, but the relativistic kinetic
The Hydrogen Atom 201

energy Correction ensures that levels characterized by the same values of n and
j, but different values of /, are degenerate. This degeneracy persists even if the
Dirac equation for a one-electron atom is solved exactly, as will be seen in
Section 11.7.
If the notation used for a level is ni; the first few levels are:

Isi(k= +1)
[2s (kK = + 1), 2ps(k = — 1), 2Paalk = + 2)
[3 (k= + 1), 3ps(k = — 1], [3panlk = + 2), 3dga(k = —2)],
3ds2(k = + 3)
= (11.32)
where degenerate levels are enclosed in square parentheses. Of course, each of
these levels has a further (27 + 1)-fold degeneracy corresponding to the poss-
ible values of m;, but this degeneracy is only removed by an external magnetic
field. Finally, it should be noted that, although the Dirac theory predicts that,
for example, the 2s1 and 2p levels are degenerate, experiment shows that in
the hydrogen atom the 281 level has a slightly higher energy than the 2p1 level.
This effect, which is called the Lamb shift, may be explained by quantum
electrodynamics and is considered briefly in Section 11.9.

11.3. The simultaneous eigenfunctions of j cayeid incense ifs WS

In the preceding section use was made of basis functions which are eigenfunc-
tions of the operators j”, 1”, s”, K andj,, but they were not related explicitly
to the original basis functions which are eigenfunctions of J”, s”, J, and s,. Their
identity must now be considered and a number of additional properties estab-
lished, since they are to be used in the exact solution of the Dirac equation.
Since they are linear combinations of the original basis functions, they must
be two-component functions, which can be written as:

pe (ob (11.33)
W2

where W, and W» are functions of space coordinates only; in this form yp is

automatically an eigenfunction of s* with eigenvalue s(s + 1) = 3/4. It is also
an eigenfunction of I? with eigenvalue /(/ + 1), if the two components , and
W> are both chosen to be a product of a radial function and spherical harmonics
of the same degree:
202 Advanced Molecular Quantum Mechanics

Wi =: AiT)Yim, 4, >); W2 = De) GeACe ¢). ¢! 1 34)

The relationship between m, and m; may be established by using the condition

that y is to be an eigenfunction of/,:

i. ie\ a ' ty1 tO | 3) pS bsaka Bits tak (11.35)

V2 QO, Lg V2 (, — 2) 2 V2

where Equation 11.18 and the matrix representation (Equations 1.36) of o,

have been used. Reference to Equations 11.9 and 11.34 shows that m=m +1
and that m; = m,+3.
The next stage is to show that the radial functions, f,(7) and f,(7), can only
differ by a constant. To do this use is made of the operator K (Equation 11.20),
which can be written as a two-by-two matrix with the aid of the matrix repre-
sentations of the components of oe:

TAP sea is Wi
Ky = =k ; (11.36)
hy auhl 1 aoa W2 V2

Expansion of this relation gives two equations connecting W, and W2, but only
one is needed:
C1 + L)Wit Ue — ily2 = ky. (11.37)
On substitution for ~, and W2 (Equations 11.34) and use of Equations 11.9
and 11.10 this gives:

(k= m,— fy = (C+ m+ 10 mp ]*h. (11.38)

Thus f, and f, only differ by a constant and w can be written as:

y= fy, (11.39)
where
C1Y im,
X= : (11.40)
C2Y 1,m)+1

The constants c, and c2 may easily be obtained, since their ratio is given by
Equation 11.38 and, if f(r) is normalized, normalization of y requires that
|e,|? + |egI?=1. In quoting the results two possibilities may be recognized
depending on whether & is greater than or less than zero; these two cases are
distinguished by a superscript + or —, respectively. For k positive (Equations
11.26a):
The Hydrogen Atom 203

V = fOXim;= 10 ("
a0cae ‘) (11.41)
where ari
= [Gt+mp/yP?; ck = [G—m) /2/}3, (11.42)
while for k negative (Equations 11.26b):

1Yj+4 ,m; =2
Y TUX: = ro (° ia | (11.43)
C2 j+h, my+3
where

= [(J—mjt+D2UG+DP; of = —[G+m,t+D2G4+
Di. (11.44)
It is also easy to confirm that these two-component angular functions
es behave in the expected manner under the various operators:

DXi ede Ny = MXimn;>

hsXiny = jamGea + 1)}?x?rape es
iXim, = (G+ myi-m; + DPX; pt
6 ied 2 Oi | Clas Xm;
There is one other property of these functions which is needed later, and
this concerns their behaviour under the operator (¢.r)/r, which is the radial
component of @. It is easy to show that this operator commutes with j, but
anticommutes with K. Consequently, the result of SUCISUNE on een with
(o.r)/r is a function which is also an eigenfunction of j? and j, with thé same
quantum numbers j and m,, and which is an eipenuncsion of K but with an
eigenvalue differing by a factor of — 1 from that of aa . Thus:

(OX; = pao cot (11.46)

where Tim, is a constant that must now be determined.
It may first be shown that Bim is independent of m;, since from Equations
11.45 and 11.46:

je (0-2)7} Xm, = (A mG+my+ VIP AjmjX; myers 11-47)

while
[ConrlisXn, = [GF — mG + mj + 1}? 4, mj+1X} yeanill48)
Now, since (¢.r)/r and 7, commute, Tim, is the same as Gj m+ and in future
the eigenvalue of j, may be omitted.
204 Advanced Molecular Quantum Mechanics

To evaluate a; the special case when 9 = 0 is considered; the operator

(o.r)/r is then just 0,, while for a spherical harmonic:

Yim(@ = 0) = (22+ 1)/47]?5

my, (11.49)
so that from Equations 11.41 to 11.44:

xX; | dia ue 11.50

jmj (6 =0) = [G+ 3)/4a]? A bytes (11.50)

Thus for 6 = 0:

+ + 1 a ! 0 Smj,+4
lone
x ae eina — ss =
ml j
alan)
= 2
ie cea

had
= [Gi[7+ + 3)/47]
D/Any? Eads = Xing
x? (11.51 )

so that aj = 1. The required result is therefore:

(OLXin = Ximp-
J
(11.52)
since, although it has been determined for the special case 9 = 0, aj is a con-
stant and independent of 0, as may be seen by noting that the square of (o.r)/r
is just 1 by Equation 8.40.

11.4 Commutation relations for the Dirac Hamiltonian

In a one-electron atom the electron experiences no magnetic potential, so that

the Dirac Hamiltonian is:
H = Bmc? + ca.p— ed, (11.53)
where the electric potential ¢ is Ze/4meor. Since ¢ commutes with the orbital
angular momentum operator Al, the results of Section 8.4 for a free electron
still hold and # does not commute with | or o. However, H does commute
with the total angular momentum j (Equation 11.18) and consequently the
eigenfunctions of the Dirac Hamiltonian are also eigenfunctions of the oper-
atorsj*and j,.
Although the Dirac Hamiltonian also commutes with o?, it differs from the
non-relativistic case in that it does not commute with /? oro.1. Nevertheless,
the new operator:
K = B(o 1+ 1) (11.54)
The Hydrogen Atom 205

does commute with H, j? and j,, and may also be used to classify the eigen-
functions of the Dirac Hamiltonian. It is similar to the operator (Equation
11.20) used in the non-relativistic theory and is denoted by the same symbol,
but since K now possesses a four-by-four matrix representation no confusion
should arise. It may be noted that the operator B(¢.1) does not commute with
the Dirac Hamiltonian and the non-relativistic operator was chosen to be
(o.1+ 1) rather than oI so that the same eigenfunction k can be used in both
the exact and the approximate theory.
Since H, j*, 7, and K all commute with each other, the solutions of the
Dirac equation are simultaneous eigenfunctions of these operators. However,
an eigenfunction Y must now have four components and may be written in
terms of two two-component functions, W, and W_:

We
v= | ) (11.55)

Since W is to be an eigenfunction of j*,j, and K (Equation 11.54) with eigen-

values j(j + 1), m; and k, respectively, , and W_ possess the following proper-
ties:
Ws IU + 1s;

J2V, = MV; (11.56)

(ol ats l)Ws = +t kw A

The last of these three relations is obtained by using the explicit form of the
Dirac matrix 8; here the operator (0.1 + 1) has a two-by-two matrix representa-
tion and is just the operator (Equation 11.20) used earlier. Comparison of
Equations 11.56 and 11.45 now shows that the two-component functions
W, and W_ may be taken to be the functions 11.41 and 11.43 of the previous
section; again two possibilities arise depending on whether k is positive or
negative. Explicitly:

. -|ie2 epee (11.57)

y- BOX;
where the upper signs refer to kK=j + 5 and the lower to kK= —(j + +).
Finally, we may record that the result of (¢.r)/r operating on these four-
component functions is:

LOX;imj \ TOONjm; a: \_ (11.58)

too age) a
206 Advanced Molecular Quantum Mechanics

This result may easily be derived by using Equation 11.52 and recalling that
the four-by-four matrix representation of o is just the direct product of the
two-by-two representation with the two-by-two unit matrix.

11.5 The Dirac equation in polar coordinates

The components of the solutions of the Dirac equation have now been expressed
as the products of radial and angular functions. To proceed further it is neces-
sary to express the Dirac Hamiltonian itself in polar coordinates. Substitution
of Equation 11.57 into the Dirac equation will then give equations for the
radial functions f(r) and g(r).
To perform the transformation to polar coordinates, we use the fact that,
from Equation 2.38:
r,t, V) =20.V)—rVv. (11.59)
Rearrangement of this equation shows that the operator V may be split into a
radial and an angular part:

V = (/)[rV)—r,
0, V)I. (11.60)

The radial part involves (1/r)(r.V), which may readily be shown to be just
(0/dr), while the angular part contains (r , V), which is related to the orbital
angular momentum operator Al. Thus, the operator (a.p) is given by:

a.p = —ihaV = —(ih/r)(a.1)(0/dr)— (h/r?)ar, 1). (11.61)

The way in which the angular functions behave under operators involving
o is already known and Equation 11.61 can be rewritten in terms of o by re-
calling that « = po (Equations 8.19). In addition, the relationship 8.40 shows
that:
(o.r)(o.1) = io(r ,)), (11.62)

where the fact that r.] vanishes has been used. Finally, multiplication of both
sides of Equation 11.54 by 6 followed by rearrangement gives:

o.1 = 6K—-1, (11.63)

so that Equation 11.61 becomes:

a.p = — (ih/r)p(o.r)(0/dr— (1/r)(BK— 1)]. (11.64)

Substitution of Equation 11.64 into Equation 11.53 now gives the Dirac
Hamiltonian in polar coordinates:

KH = Bmc* — Ze?/4n€or — (ihc/r)p(o.r)[3/8r — (1/7)(BK — 1)]. (11.65)

The Hydrogen Atom 207

In seeking solutions of the equation HW = EW, substitution of Equation 11.57

for Y and use of the explicit forms of the Dirac matrices 6 (Equation 8.23)
and p (Equation 8.25) yields a pair of coupled two-component equations. The
way in which the two-component angular functions behave under the operators
(o.r)/r and (6.1 + 1) is given in Equations 11.58 and 11.56, so that:

[(mc? — Ze?/4n€or — E)f — (ihic/r)(k + 1)g — ihe(g/ar)\x,,,. = |

j (11.66)
[((— mc? — Ze?/4neor — E)gt (ihic/r)(k — 1)f — ike(af /ar)| Xm;
The angular functions are now just multiplicative factors and may be dropped.
The resulting radial equations are simplified by using two new functions:

Fo = pf: G = irg. (11.67)

If, in addition, the fine structure constant a and the energy parameter €
(= E/mc’) are introduced, then after division throughout by fc the equations
become:
[(mce/h)(1 — €) — Za/r|
F — (0G/dr) — kG/r 0
(11.68)
[—(mce/h)0 + €) — Za/r|G + (OF /ar) — kKF/r Il 0}.

These equations may be checked by considering their non-relativistic limit,

when the coefficient of G in the second equation is of the order of — 2mc/h
so that:
G = h(dF/or
— kF/r)/2mc. (11.69)

Substitution of this into the first of Equations 11.68 now gives:

07F lar? — k(k — 1)F/r? — (2mce/h)[(me/h) — €) — Za/r]F = 0, (11.70)

an equation which may be identified with the usual non-relativistic radial
equation by replacing F by rR, identifying k(kK— 1) with /(/ + 1) (Equation
11.23) and allowing for the different energy origins.

11.6 Solution of the radial equations

To solve the radial equations (11.68) series solutions are sought, but in doing
this two conditions may be imposed. First, we may restrict ourselves to bound
states, so that € (= E/mc’) is less than unity. Secondly, for bound states it
must be possible to normalize the eigenfunctions.
A starting point for the solution is provided by solving the radial equations
for the special case when r tends to infinity and they reduce to:
208 Advanced Molecular Quantum Mechanics

(dG/or) ee
= (mc/h)
hi — €)
—e)F Mie

(OF /or) = (mc/hA) + €)G).

These equations may be uncoupled by substituting one in the other to give

two second-order equations:
(80°F /dr?) =~ (me/h)*(1 — &)F;
(11.72)
(8°G/dr?) = (me/h)*(1 — €”)G,
the normalizable solutions of which are:

F ~ cp exp [—(me/A(1 — €?)?7];

sis (11.73)
G’= te exp [—(nc/Ayl = e?)?r] ;

the original equations (11.71) show that the constants cp and Cg are related by:

crleg = —(A+0/A—©)]?. (11.74)

For bound states it is clear from the definition of e that F and G are both real
and that cr > cg, so that the components of y, and W_ may again be thought
of as the large and small components, respectively.
The solutions (Equation 11.73) for very large r suggest that the substitu-
tions:
F = (1 +) exp (— p/2)u + v);
(11.75)
G = (1—€)? exp (— p/2)(u—v)
may be appropriate, where u and v are new functions of rwhich, because of
Equation 11.74, are subject to the condition that v> u when r tends to infinity.
In Equations 11.75 the new dimensionless variable:

p = (2mc/hA)\( — e)2r (11.76)

has been introduced; no confusion should occur between this and the Dirac
matrix which has the same symbol. Substitution of Equations 11.75 into Equa-
tions 11.68 followed by rearrangement and cancellation of the exponential
terms gives equations in (u + v) and (wu — v), but by addition and subtraction a
pair of coupled equations in u and v themselves are obtained:

du/dp = [po —Zae(1 — €?)-?](u/p) + [k —Zol1 — €)?] (v/p)

Wheic)
2](u/p)
dv/dp = [Zae(1 — €*) ?](v/p) + [k + Za(1 — €?)

We now investigate the possibility that u and v may be written as ascending

power series in p:
The Hydrogen Atom 209

lag ik PA a a A ee (11.78)
where one (or both) of ag and bo is non-zero. Substituting in Equations 11.77
and equating the coefficients of p**”"! on the two sides of the equations gives:

(A+ va, = ay_;—Zae(l — €?) 2a, + [k—Za(1 — €)"2]b,

; : (1179)
(A +v)b, = Zae(1 —e€?) 7b, + [k + Za(1 —e?) 2 Ja,
For the special case v = 0, the coefficient a,_, is zero by definition and a pair
of coupled equations in ag and bp results:

|At Zac1—e?)?, —[k—Za(l— males

b = 0. (11.80)
A— Zae(1 — ey?
[k + Za(1 = ey 2]
+
: 0
For non-trivial solutions of these equations both ao and bo must in general be
non-vanishing, so that the series u and v both start at the same power of p. To
determine this power, that is to determine the value of A in Equations 11.78,
use can be made of the fact that for non-trivial solutions the determinant of
the two-by-two matrix in Equation 11.80 must vanish. Expansion of the de-
terminant gives a quadratic equation in A, the solutions of which ‘are:

h = +(k?—Za2)?. (11.81)
A decision may be made between the two possibilities for A by invoking
the condition that the eigenfunctions of the Dirac Hamiltonian must be nor-
malizable for bound states. Since the angular functions are already normalized,
this normalization condition reduces to one for the radial functions:

SCP + le Ard = f(F?+G%a = 1. (11.82)

Here use has been made of Equations 11.57 and 11.67 and the fact that F and
G are both real; the extra factor of r? on the left-hand side of the equation
comes from the volume element in polar coordinates. Now as p approaches
zero (F? + G”) behaves as p”* and for the normalization (Equation 11.82) to
be possible \ must be greater than — x. Since the minimum value that k? may
adopt is + 1, the positive solution for ’ must be taken. (For k?=1andZ>
119 the negative solution cannot be excluded, but this possibility may safely
be ignored until superheavy elements have been made.) Thus for atoms with
low atomic number A is approximately |X|.
To investigate the coefficients a, and b, further it is convenient to define a
new dimensionless quantity:

n’ = —A+Zae(1 — &)?. (11.83)

210 Advanced Molecular Quantum Mechanics

From the second of Equations 11.79 the ratio a,/b, is seen to be:

a,|by = —(n'—v)/[k+Za(l —€?)2] = +(n'—v)aoln'bo, (11.84)

while use of this result with the first equation gives, after some manipulation,
the recurrence relation:

dy = =(N' — v) ap, (PQA4P). (11.85)

This equation leads to the general expression for a):

= (—1)’(n' —vyn’ —v + 1)...( — lao

ay
yi(2d + y(2A+v—1)... (2X41) (11.86)
and a similar expression for b, may be obtained using Equation 11.84:

mG. 1)’(n'—v+ 1)(n' —v +2)... 1n'bo

? ~~ plQA4+v\Qd+v—1)...QX4+1) are)
The ratio of a and bo is given by Equation 11.84, but their actual magni-
tude is determined by the normalization condition (Equation 11.82). However,
although A has been chosen so that F and G do not diverge as r approaches
zero, their behaviour when 7 becomes infinite has yet to be considered. In
particular the series u and v must not diverge faster than exp (— p/2) converges
as r increases. For large values of v both a,/a,_, and b,/b,_, are approximately
1/v, so that the series u and v both behave as exp (p) and F and G diverge as
exp (p/2). This behaviour prevents the normalization that is necessary for
bound states, but may be avoided by insisting that both the series u and v ter-
minate at a finite value of v. Reference to Equations 11.86 and 11.87
shows that this only happens if n’ is a positive integer. The series u then termi-
nates atv =n’, while v terminates at y=’ + 1.
The case when n’ = 0 requires special consideration, since, although v termi-
nates at v= 1, Equation 11.86 shows that the series u only terminates if ao
itself vanishes and u = 0. From Equation 11.84:

dolby = —n'[[k
+ Zo(1 — ey 7], (11.88)
so that this possibility is acceptable provided the denominator does not vanish
as well as the numerator n’. Now for n’ = 0:
N= (k?—Z0?)? = Zae(1 —€?)?, (11.89)
where Equations 11.81 and 11.83 have been used. Solution of this equation
for k gives:
k =\4 Zoli ey ?; (11.90)
The Hydrogen Atom ail

for the negative solution the denominator in Equation 11.88 vanishes and
ao/bo is indeterminate, but the positive solution is permissible. Thus there are
solutions for n'=0, but they are only allowed if the quantum number k is
positive.
To complete the solution of the radial equations for bound states it is only
necessary to normalize the radial functions, that is to determine the magni-
tudes of do and bo. This is not a trivial problem, since F and G involve an ex-
ponential and, because A is non-integral, fractional powers of p. Nevertheless,
normalization is possible using gamma functions, which have to be evaluated
numerically and may be obtained from tables; the inclusion of the details here
would serve little purpose.

11.7 The energy levels

Although the eigenfunctions of the Dirac Hamiltonian have now been deter-
mined, the eigenvalues E (= emc”) have yet to be found. Now from Equation
11.83:
e(1—e)? = (n' +)/Za, (11.91)
where A is (k?— Za”)? and n’ is a positive integer or zero. Solution of this
equation gives:
E = mc’e = mce?[1+ (Zaf(n’ +d))’]?. (11.92)
At this stage it is convenient to introduce:

n=nt+kl. (11.93)
Since n’ = 0, 1,2,...and the minimum value of |k| is + 1, the new quantum
number 7 can be any positive integer but not zero. In addition, for a given
value of n the maximum value that |k| can take is n, although k = — n is not
allowed, since this corresponds to n' = 0 for which k cannot be negative. Thus,
the possible values of k for a given n are 1,2,...,n if k is positive and — 1,
—2,...,—(n—1) if k is negative. When it is recalled that k is +(j + +), it
may be seen that j, k, and n can have just the same values as in the approximate
two-component theory (Equations 11.26) and in particular the new quantum
number 7 may be identified with the non-relativistic principal quantum num-
ber 7. In the four-component theory / is no longer a good quantum number,
although the large and small components, y, and W_, are separately eigenfunc-
tions of /* as may be seen from Equations 11.41, 11.43 and 11.57. It was for
this reason that the quantum number k was introduced earlier. Nevertheless,
it is convenient to use the notation 11.32 for the different levels, the / value
for the large components being employed.
212 Advanced Molecular Quantum Mechanics

Substituting for n’ and A in Equation 11.92 gives finally for the eigenvalues:

E = mea + [Zal(n— |k| + (kK?—Z707)?)]?2. (11.94)

This may be expanded as a power series in (Za)?:

E = me?[1 —Z?a?/2n? — (Z%04/2n)(1/|k| — 3/4n) + O(Z °a®)]; (11.95)

since |k| = ( + 4), this is the same result as that obtained earlier (Equation
11.31). However, as Z increases such an expansion becomes less satisfactory,
since the expansion parameter gets larger, and the exact solution (Equation
11.94) should be used.
As for the approximate theory, the exact energy (Equation 11.94) only
depends on n and |k\, so that degeneracies arise as shown in 11.32.
These degeneracies occur because in a one-electron atom the potential ex-
perienced by the electron is Coulombic; in many-electron atoms this is no longer
true and the degeneracies are removed. However, even in one-electron atoms
some of the degeneracies are lifted by the Lamb shift, which is the subject of
Section 11.9.

11.8 Comparison of Dirac and non-relativistic atomic orbitals

The eigenfunctions of the Dirac Hamiltonian, which may be said to represent

Dirac orbitals, are four-component functions in contrast to non-relativistic
atomic orbital functions, which have one component, and the two-component
functions of the approximate theory.
It has already been seen that for bound states the two components of a
Dirac eigenfunction involving the radial function F are the large components,
while those involving G are the small components. The ratio of the amplitudes
of the small and large components thus has the approximate magnitude:

GIF ~ {1-6/4 + 6), (11.96)

where Equations 11.75 have been used. Substitution for € and expansion of this
ratio as a power series in Za then gives:

G/F =~ Za/2n; (11.97)

classically this is just the ratio of the Bohr velocity of the electron to the
velocity of light. This shows that for light nuclei the small components are
indeed not very important, but for large Z their influence is not negligible.
For instance for Z = 80 and n = 1 the ratio of the small components to the
large components is approximately 0.3. Even when this is squared to give the
The Hydrogen Atom 213

ratio of the contributions to the probability density, it is seen that the small
components are responsible for about ten per cent.
To compare and contrast relativistic and non-relativistic atomic orbitals,
approximate Dirac eigenfunctions for n= 1 and n=2 are used. These are
given in the table and are correct to order Za. They are normalized to this
order provided each is multiplied by the factor 12(Z/ao)?”, where do is the
Bohr radius; in addition, the dimensionless parameter p (Equation 11.76) is to
this approximation just Zr/ao, the same quantity as that employed in the non-
relativistic theory (Equation 11.6). Although these functions become less ac-
curate as Z increases, they exhibit the same qualitative features as the exact
functions, and are easier to handle; the results obtained may be generalized to
higher values of 7 without difficulty.
The probability density distribution |W|? is the real interest, but radial
parts of the individual components of W are considered first; the angular parts
involve spherical harmonics and do not need special consideration. For each
four-component function there are two radial functions, one for the large
components f(r) and one for the small components g(r). For f there are n’ or
(n' —1) nodes in the radial function depending on whether k is positive or
negative, respectively. If the value of / appropriate to the large components is
used, we may say that f has (n —/— 1) nodes. This result is the same as that
for non-relativistic orbitals and indeed, to the order of accuracy used in the
table, the radial functions of the large components are the same as those in the
non-relativistic theory. For g the number of radial nodes is n’ regardless of the
sign of k; this means that when k is positive the large and small components
have the same number of radial nodes as each other, and in the special case
when n’ = 0 and k can only be positive f and g are both nodeless. The impor-
tant thing to note is that, although the large and small components may have
the same number of radial nodes, a node in g never occurs at the same value of
p as a node in the corresponding radial function f.
When | |? is considered it is immediately apparent from the table that it
may be factorized into a radial and an angular part. This is because, although
|W,|? and |W_|* have different radial dependences, their angular behaviour is
similar and the ratio of |W,|? to|W_|?is independent of @ and ¢.
The radial part of |W |? is thus a linear combination of ||? and |g|?. Since
the large components predominate, the radial dependence is very like that of
the corresponding non-relativistic orbitals, but unlike these the Dirac orbitals
have no radial nodes. Although f has nodes at the same places as the corres-
ponding non-relativistic radial functions, g never vanishes at these points. As
an example the 2s: orbital may be considered. At p = 2 both fand the non-
relativistic 2s radial function possess a node, but the node in g occurs at
Table 11.1. Eigenfunctions of the Dirac Hamiltonian, for a one-electron atom
correct to order Za. Each function should be multiplied by a factorm 2(Z/ao)*””,
where dg is the Bohr radius; p is the dimensionless parameter Zr/do.

Is: (n= lj=z,k=+1,n = 0)

Mate
Ge \

e?

1. By
3iZae” cos 0 siZae
1. —9
sin= 0e7'*
=

1. - ° i 1. =
5iZae ? sin be’? — ziZae™? cos 0

281 (n= 2,7=7,k=+1,n'=1)

eP(1 — p/2)
1 0 1 e?( 1 — p/2)
2/2 siZae "(1 — p/4) cos 6 2V2 | tiZaé?(1 — p/4) sin de!
5iZae°’?(1 — p/4) sin be!% — siZaé’?(1 — p/4) cos 0 /

m= + 5 aye tell
Wy ne
e °/20 cos 0 e-/29 sin Oe*
1 e-P/2sin A el? 1 — e256 cos 0
4V6 \ —(3/2)iZae"(1 — p/6) 4/6 0

0 — (3/2)iZaeP"(1 — p/6)
The Hydrogen Atom 2V9
2Paa(n = 2,j= 3/2, k= + 2,n'=0)

m; = +3/2 iy = 3/2
e °’? sin Oe!” 0
1 0 1 | eo sin 6e7%?
8 | (1/4)iZae~’*p sin 0 cos be!* 8 (1/4)iZae~?’?p sin? Oe?
(1/4)iZae~?!?p sin? Oe? —(1/4)iZae?”p sin 6 cos 0e*%

m, = +3 m; = —%
e °? » cos 6 56°/29 sin Oe 1%
1 |—3e?? p sin Oe? 1 |e?"p cos @
4/3! — (1 /8)iZae”’?p(1 —3 cos?4) 4/3 (3/8)iZae~?p sin @ cos de %?
(3/8)iZae~?’*p sin 6 cos be!” (1/8)iZae™?’?
p(1 —3 cos?
6)

p=4. In fact jg|* at p =2 is of the order of (Z/ay)°Za? exp (— 2)/8 and,

although this is very small, it ensures that the 251 orbital is radially nodeless.
Another qualitative feature of the radial part of Dirac orbitals is that the
probability charge distribution is slightly contracted compared with the corres-
ponding non-relativistic orbitals. This cannot be seen from the approximate
functions in the table, since the effect is of higher order than Za. However, it
might be supposed that, since the inclusion of relativistic effects leads to a
slight lowering of the electron’s energy, this corresponds to the electron being
on average closer to the nucleus. This naive argument also suggests that the
contraction should be more marked for |kK|= 1 and for low values of n; de-
tailed consideration of the exact eigenfunctions shows that these statements
are correct.
The angular dependence of Dirac orbitals has yet to be considered. Unlike
the radial part it is not influenced by the small components, since |p,|’and
|w_|? are both proportional to the same angular function. We will see that, in
contrast to non-relativistic orbitals, there are no angular nodes, but this is to
216 Advanced Molecular Quantum Mechanics

j=3/2,\mz\/2
(1+3 cos®@)

j=3/2, \mp=3/2
4sin2@

/=5/2, l= 3/2
sin@@ (16-15 sin@@)

Fig. 11.1. The angular distribution for selected Dirac orbitals. Each is cylin-
drically symmetric about the z axis.

be regarded as being the result of a correct handling of spin using two-com-

ponent wavefunctions as in Section 11.3.
The first thing to note is that the probability density distribution associated
with a Dirac orbital is independent of the polar coordinate ¢, so that Dirac
orbitals are all cylindrically symmetric about the z axis. In addition, the angu-
lar dependence of |W|? depends only on the quantum numbers jand m,;; for
example, when j = 5 the orbital is spherically symmetric as may be seen ex-
plicitly for 1s1, 2s: and 2p: by reference to the table.
When the value of j differs from S, the angular dependence is more compli-
The Hydrogen Atom PAVE)

cated, but two limiting cases may be distinguished. For |m;|= 5 the angular
dependence resembles a dumb-bell with its axis along the z axis; for j = 3/2
the angular part of |W |? is proportional to (1 + 3 cos? 0) and is plotted in Fig.
11.1. At the opposite extreme, when |; | takes its maximum value of/, the
distribution is toroidal and an example of this case is also given; the specific
case shown is also for j = 3/2, the angular dependence being proportional to
4 sin’ @. For intermediate values of m, the orbitals are also toroidal, but with
a number of lobes, the example in the figure being for 7= 5/2 and m, = 3/2,
for which |W |? is proportional to sin? (16 — 15 sin? 6).
Although the first angular function shown in the figure is not unlike that of
a non-relativistic p, orbital, it has no node perpendicular to the z axis. The
other angular functions are also nodeless, since they are cylindrically symmet-
ric about the z axis. The lack of angular nodes is a general property of Dirac
orbitals. |
We have already seen that relativistic orbitals have no radial nodes, so that
it may be concluded that except at the nucleus itself they have no nodes at all;
there are no radial nodes because the eigenfunctions of the Dirac Hamiltonian
have four components and the small components prevent them occuring, while
the lack of angular nodes may be attributed to the fact that the electron has
spin .
This is in sharp contrast to non-relativistic orbitals, which in general have
both angular and radial nodes, a feature which raises the question of how an
electron gets from one part of an orbital to another, if there is a node in be-
tween. However, this problem no longer arises if relativistic atomic orbitals are
used, since they are nodeless.

11.9 The Lamb shift

Both the exact (Equation 11.94) and approximate (Equation 11.95) eigen-
values of the Dirac Hamiltonian for a one-electron atom show that levels
characterized by the same values of the quantum numbers n and j are de-
generate. However, this degeneracy is in fact removed by the Lamb shift,
which is of quantum electrodynamic origin. The largest manifestation of this
effect occurs for the m = 2 levels in the hydrogen atom and is illustrated in
Fig. 11.2, which shows the successive effects on the non-relativistic energy of
including relativistic effects and the Lamb shift; the energy separations are
given in terms of frequency (1 GHz = 10?Hz = 0.03336 cm‘) and are to be
compared with the non-relativistic energy lowering of 8.22 X 10°GHz relative
to the rest energy of the electron.
218 Advanced Molecular Quantum Mechanics

n=2

\
VeNS 2:737 GHz
ene
ty ars sitive, Sse
\ 2 Pyjp(k=2)
\
\
\
\
\
\
\
\ 10-949 GHz
\
\
\
\
\
\
25,9 (A=N)
-

\ Be 1-058 GHz
Se ee eee ee eee
22172 (k=-1)

Non-relativistic Relativistic Lamb shift

Fig. 11.2 The effect of relativistic corrections and the Lamb shift on the
energies of the n = 2 levels in the hydrogen atom.

Although the Lamb shift is a quantum electrodynamic effect and cannot

be explained fully here, an attempt will be made to indicate its origin, since
at least two authors have wrongly attributed it to the Zitterbewegung of the
electron. As we have seen, the concept of Zitterbewegung arises when the non-
relativistic approximation to the Dirac Hamiltonian is used (see Section
8.10). The Darwin-type term then accounts for the correction to the
electrostatic interaction energy between the nucleus and the electron due
to the smearing out of the electron’s charge that is associated with the Zitter-
bewegung; this correction term was included in the approximate theory of
Section 11.2. However, if the Dirac equation itself is solved this effect is
automatically accounted for and mention of the Zitterbewegung is out of
place and misleading. Moreover, the relativistic corrections to the energy are
of order mc?Z*q* and in particular the Darwin-type correction term in the
approximate theory may be seen to be of this order by reference to Equation
11.29. The Lamb shift, on the other hand, is smaller than this by one order
in a.
The confusion has arisen because an estimate of the magnitude of the
Lamb shift may be obtained using arguments similar to those used in Section
8.10 to explain the Darwin term on the basis of the Zitterbewegung. There
The Hydrogen Atom 219

it is shown that, if the electron has a highly oscillatory motion superimposed

on its mean position r, then the correction to an electrostatic interaction
energy — e@(r) is given approximately by:

— e(5*)
V7 o(r)/6, (11.98)
where ¢(r) is the scalar potential and & is the instantaneous deviation of the
electron from its mean position. For the Zitterbewegung the time average
(8*) is of the order of (A/mc)?.
The Lamb shift may be thought of as arising from an additional smearing
out of the electron’s charge that is superimposed on that due to the Zitter-
bewegung. This arises from the quantization of the electromagnetic field,
which is the subject of the next chapter. Nevertheless, we may anticipate this
discussion to the extent of recognizing that the quantized field has zero-point
energy in the same way that a quantized harmonic oscillator does. This result
is not unexpected, since the classical field may be described in terms of a
collection of classical harmonic oscillators (Section 6.7). Consequently, even
a field-free vacuum contains electromagnetic energy in the form of so-called
‘vacuum fluctuations’, which interact with the electron and cause it to under-
go a rapid random motion. Detailed calculations, which cannot be presented
here, show that for an electron in an atom the mean square deviation of this
random motion is:
(5?) = (2a/7)(h/mc)*|n(2n?/a*), (11.99)
which is smaller than that due to the Zitterbewegung by one order in a.
If the result (Equation 11.99) is accepted, the crude model of Section
8.10 may be used to estimate the magnitude of the Lamb shift. In addition
to (57) the expression 11.98 involves V7¢(r) and in a one-electron atom this
is just — Zed(r)/E9 as may be seen from Equation 11.15. Thus the Lamb
shift is given by the operator:

(e?Za/37€9)(h/mc)?5(4)In(2n?/a’). (11.100)
The expectation value for an electron in a non-relativistic s orbital with
principal quantum number n is from Equations 11.11 just:

mce?Z*a5(4/31n?)In(2n?/a’), (11.101)
while in other atomic orbitals it vanishes. Although the model used is crude,
more sophisticated approaches give the same result for non-relativistic
orbitals.
For the hydrogen atom 11.101 gives 1.040 GHz for the Lamb shift of the
2s level; the 2p levels are unaffected. This is to be compared with 1.058 GHz,
220 Advanced Molecular Quantum Mechanics

the experimental separation of 251 and 2p:. The discrepancy has been ex-
plained to within 1 MHz by relativistic, higher-order quantum electrodynamic
and other effects. These corrections also produce small shifts in levels other
than s levels. Lamb shifts have also been observed in the hydrogen atom for
n>2 and in other one-electron atoms and they have all been explained
quantitatively. They also occur in many-electron systems, but are more com-
plicated; electron-electron interactions are of course present and full calcu-
lations have only been performed for the simplest species.

11.10 More complicated systems

So far this chapter has been devoted to the relativistic treatment of one-
electron atoms in which the nucleus is assumed to be stationary and spinless.
It has already been remarked that the finite mass of the nucleus may largely
be accounted for by using a reduced mass for the electron and, except for
a few remarks about the influence of nuclear spin, this section is concerned
with many-electron atoms.
The presence of a nuclear spin magnetic moment in a one-electron atom
may be effectively allowed for by using perturbation theory, since the cor-
rections introduced are relatively small. If non-relativistic atomic orbitals are
employed as spatial basis functions, it is appropriate to use a perturbation
based on the approximate Hamiltonian of chapter 10. In particular the
nuclear hyperfine interaction arises from the Fermi contact term (10.6f); the
dipole-dipole term averages to zero for an atom because of its spherical sym-
metry. However, it is only permissible to use first-order perturbation theory
for the Fermi contact interaction, since it has its origin in the Breit operator.
Indeed, for the hydrogen atom the estimated hyperfine splitting is infinite if
second-order perturbation theory is used, although the cause of this diver-
gence has also been attributed to treating the proton as a point particle.
An alternative approach is to employ Dirac atomic orbitals but, although
it is tempting to use, for example, the Fermi contact operator as a pertur-
bation, this is not permissible, since it is a non-relativistic operator. If it is
used, even first-order perturbation theory gives infinite answers, since Dirac
orbitals with 7= 4 have weak singularities at the nucleus as the exact radial
functions of Section 11.6 show. The correct procedure is to substitute the
vector potential due to the nuclear spin magnetic moment into the Dirac
Hamiltonian. This gives:

(Son e/4megc)a(ly ,1)/7? (11.102)

as the perturbation, where « is the Dirac operator. Exact diagonalization of
The Hydrogen Atom p54

this operator using all Dirac orbitals with the same n as basis functions gives
the same results as the non-relativistic theory except for a correction of rela-
tive order (Za)*. For example, the correction factor for the 1s: level is
(1 + 3(Za)?/2 +... .); correction factors for other levels have been tabulated
in the literature, but except for large Z they are relatively unimportant.
For many-electron atoms perturbation theory must again be used to esti-
mate the effect of small terms in the Hamiltonian, such as those involving
nuclear spin. However, the choice arises as to what electronic basis functions
to use. The usual approach is to obtain eigenfunctions of the non-relativistic
Hamiltonian, which consists of the kinetic energy of the electrons and all the
Coulomb interactions. Even these can only be obtained approximately and in
general consist of a linear combination of determinants involving one-electron
functions that have been optimized using a self-consistent field criterion, the
starting point for the iterative procedure being eigenfunctions for one-electron
atoms. For inner electrons and heavy nuclei the relativistic corrections are
relatively large and their calculation by perturbation theory is not very satis-
factory. This is becoming a serious drawback, since attention is now being
focused on inner electrons by the use of experimental techniques such as
X-ray photoelectron spectroscopy. This situation has led to the use of the
Dirac Hamiltonian for the individual electrons, since allowance for the relati-
vistic corrections involving individual electrons is then automatic; in particu-
lar, account is taken of such things as spin-orbit coupling and the relati-
vistic corrections to the kinetic energies of the electrons. An appropriate
procedure is described briefly here; for the details reference must be made
to the research literature, since the mathematical techniques used are outside
the scope of this book.
The approximate Hamiltonian for a many-electron atom may be taken as:

eee l t
E e7/4n€or ij,
J
(11.103)

where H; is the Dirac Hamiltonian for electron 7 and includes the Coulomb
interaction between the electron and the nucleus. The term representing the
Coulomb interaction between the electrons is not even approximately Lorentz
invariant, but the terms that have been omitted from the full Hamiltonian
may be treated as perturbations on the eigenfunctions of 11.103. Indeed,
to describe the interaction between two electrons better the Breit operator
9.41 may be added, but as we have emphasized repeatedly it is only ap-
propriate to use it in a first-order perturbation treatment. Other perturbations
that could be included are those involving the nuclear spin magnetic moment
and quadrupole moment; electron spin is of course included automatically
in the Hamiltonian 11.103. The problem then is to find eigenfunctions of
222 Advanced Molecular Quantum Mechanics

11.103 that can be used as basis functions for the perturbation treatment.
Now the eigenfunctions of the operator 2 H; in 11.103 are just products
t

of the eigenfunctions of the individual Dirac Hamiltonians H;; these provide

suitable starting functions for an iterative procedure. Of course, these
functions are not unique since permutation of the electrons gives other eigen-
functions of © H; with the same eigenvalue so that a linear combination of
l

these products is taken. The Pauli exclusion principle restricts the possible
linear combinations to those which are antisymmetric with respect to inter-
change of any pair of electrons and this linear combination may conveniently
be written as a determinant, the elements being (four-component) Dirac
functions. For closed shell configurations only one determinant is needed, but
for open shell configurations a linear combination of determinants is neces-
sary, although the number involved may be reduced by choosing the com-
binations to be eigenfunctions of the total angular momentum operator iz

When the Coulomb interaction between electrons is introduced the exact

eigenfunctions of the Hamiltonian can no longer be written as the product of
one-electron functions, since a definite energy cannot be associated with an
individual particle and the probability of an electron being at a particular
point in space depends on the position of the other electrons. However, it is
not practicable to obtain exact eigenfunctions of the Hamiltonian (Equation
11.103) and an approximation must be made. The usual policy is to assume
that each electron experiences an average repulsive potential due to the other
electrons in addition to the attractive potential of the nucleus. With this
simplification the potential energy of an electron is a function only of its
distance from the nucleus, although the electrostatic potential is no longer
Coulombic. This approximation is not too unrealistic since for Dirac atomic
orbitals closed shells of electrons have spherically symmetric charge distri-
butions and this fact does not depend on the assumption of a Coulomb
potential.
Thus for a many-electron atom the eigenfunctions of the Hamiltonian are
assumed to be products of one-electron functions, which are themselves eigen-
functions of the operator #; + V(r;). Since a central field has been assumed,
the angular dependence of the components of the one-electron functions is
the same as for a one-electron atom and may be factored out. However, since
the potential is no longer Coulombic, the resulting radial equations cannot be
solved analytically and numerical techniques must be used. Of course the
potential energy V(r;) is an average over all the electrons other than i and a
knowledge of their radial distributions is necessary for it to be calculated.
The Hydrogen Atom P4O/e)

This means that an iterative procedure must be adopted, the Dirac orbitals
for a one-electron atom being used to calculate initial potential energies
V(r;).
The improved one-electron functions so obtained are then used to obtain
better potentials and the process repeated until a self-consistent field is
achieved. This procedure is quite laborious and in practice the whole calcu-
lation may be accomplished in one step using the variation method; this has
the added advantage that the exchange interaction is included, if determin-
ental wave functions are used.
In Section 11.7 it was seen that for one-electron atoms eigenfunctions
with the same values of m and j are degenerate. These degeneracies of one-
electron functions do not occur for many-electron atoms, since the potential
experienced by an electron is no longer Coulombic. The energy of an electron
then depends on how effectively it is screened from the nucleus by the other
electrons. The lower the value of/ associated with the large components of a
one-electron function the lower is its energy; the same situation occurs in the
non-relativistic theory.
The wave functions obtained using this self-consistent field approach are
only approximate, but they may be improved by using techniques, such as
configuration interaction, which are well established in the non-relativistic
theory of many-electron atoms.
The relativistic theory for atoms is thus similar to the non-relativistic
theory, although the details must be modified to allow for the fact that
relativistic eigenfunctions have four components; the amount of labour in-
volved is greater and the mathematical techniques employed are more sophis-
ticated. In addition, it is only comparatively recently that relativistic
calculations of atomic structure along these lines have been attempted in any
great number and at present they are by no means routine. For these reasons
the details are not given here and reference must be made to the specialist
literature.
Finally, a few comments may be made about calculations on molecules
using relativistic atomic orbitals. Since molecules do not possess spherical
symmetry, acentral-field approximation is not poss.vle and the wavefunctions
cannot be factorized into radial and angular parts. A popular approach in
non-relativistic theory is to construct one-electron molecular orbitals, which
are linear combinations of a limited basis set of atomic functions, the variation
principle being used to calculate the coefficients or other adjustable para-
meters. In principle there is no reason why this should not be done using
relativistic atomic orbitals as a basis. However, although this approach has
been used for atoms themselves, at the present time little attention appears
224 Advanced Molecular Quantum Mechanics

to have been directed towards the use of relativistic atomic orbitals to de-
scribe molecular electronic structure. Recently attempts have been made to
solve the non-relativistic self-consistent field equations for simple molecules
by using numerical techniques and in principle this approach could also be
used in the relativistic theory.

Bibliography

Solution of the Dirac equation for the hydrogen atom

Bethe and Salpeter: pages 63-70.
Corinaldesi, E., and Strocchi, F. (1963), Relativistic Wave Mechanics, North-
Holland, Amsterdam: part II, Chapters 8 and 9.
Dirac, P. A. M. (1958), Quantum Mechanics, Clarendon Press, Oxford: pages
269-273.
Rose: pages 157-181.
Sakurai: pages 122-131.

Comparison of Dirac and non-relativistic atomic orbitals

Bethe and Salpeter: pages 70-71.
Powell, R. E. (1968), ‘Relativistic quantum chemistry. The electrons and the
nodes’, J. Chem. F duc., 45, 558.
Szabo, A. (1969), ‘Contour diagrams for relativistic orbitals’, J. Chem. Educ.,
46, 678.

The Lamb shift

Series, G. W. (1957), The Spectrum of Atomic Hydrogen, Clarendon Press,
Oxford: pages 37-65.
Sikolov, A. A., Koskutov, Y. M., and Ternov, I. M. (1966), Quantum Mech-
anics, Holt, Rinehart and Winston, New York: pages 350-354.

The introduction of nuclear spin

Breit, G. (1930), ‘Possible effects of nuclear spin on X-ray terms’, Phys. Rev.,
35, 1447: relativistic corrections to hyperfine splittings.
Rose: relativistic corrections to nuclear hyperfine splittings are discussed on
pages 188-191.
Velenik, A., Zivkovic,T., de Jeu,W.H., and Murrell, J.N. (1970), ‘The
hydrogen atom in the presence of the Fermi contact interaction’, Molec.
Phys., 18, 693: a demonstration that the Fermi contact operator taken to
second order with non-relativistic atomic orbitals leads to an infinite hyper-
fine splitting.

Many-electron atoms
Grant, I. P. (1970), ‘Relativistic calculation of atomic structures’, Adv. Phys.,
19, 747: a review of relativistic calculations on atoms.
CHAPTER TWELVE

Quantum Field Theory

The classical theory of fields was developed in Chapter 6. In particular, the

electromagnetic field was considered and it is the quantization of this field
that is the subject of the present chapter, although it should be noted that
other fields may be quantized.
It is, of course, well known that electromagnetic radiation has a quantum
nature. Indeed, quantum theory originated with Planck postulating that radi-
ation of angular frequency w can only have an energy that is an integral
multiple of Aw, where h was a new fundamental constant; this was necessary
to avoid the so-called ultraviolet catastrophe for black-body radiation. A
little later Einstein explained the photoelectric effect by proposing that
electromagnetic radiation consists of massless particles, each with energy
hw.
So far we have been concerned with quantized matter moving under the
influence of electromagnetic fields and the semiclassical approach, which
treats this radiation classically, has proved quite adequate. However, this
procedure is not very satisfactory when it comes to determining what effect
the quantized matter can have on the radiation; here we are thinking particu-
larly of time-dependent processes such as the absorption and emission of
radiation by molecules. Besides, it is inconsistent to treat one part of an
interacting system quantum-mechanically and the other part classically; for
example, it is possible to design experiments which in principle would violate
Heisenberg’s uncertainty principle by observing quantized particles with
classical radiation.
The last chapter is concerned with the interaction of radiation with matter.
Here, electromagnetic radiation in free space is discussed.
22)
226 Advanced Molecular Quantum Mechanics

12.1 Quantization of the electromagnetic field

Before considering the electromagnetic field, the more familiar particle quan-
tization is reviewed, since it provides a guide for the quantization of field
variables. Classically the Hamiltonian of a particle may be expressed in terms
of its position r and its momentum p conjugate to r. Quantization may then
be accomplished by making r and p time-independent operators and in par-
ticular by identifying p with the operator — ih(0/dr). This procedure is equiv-
alent to imposing the condition that the operators p and r satisfy the com-
mutation relations:

[pi rj] Someone [Pi Dj] = [7:7] =,0. Gof =a Pez). (12.1)

The resulting energy operator is then used in the time-dependent Schrodinger

equation, HW = ihdW/dt, where the wave function W is a function of both
space and time coordinates.
This suggests that to quantize the electromagnetic field its energy should
be expressed in terms of conjugate pairs of field variables; that is, for each
pair one variable should be the momentum conjugate to the other. Quantiz-
ation may then be achieved by interpreting these variables as operators, in-
sisting that they satisfy commutation relations analogous to Equations 12.1
and allowing them to operate on appropriate wave functions.
In Chapter 6 it was seen that the gauge of the electromagnetic potentials
can always be chosen so that at all points in space the scalar potential
vanishes and the vector potential A satisfies the Coulomb gauge (V.A = 0).
Thus, the field is determined by three field variables; these are the com-
ponents of the vector potential, which is given by Equation 6.65:

AC 1) = & [taMAralr)
+ diaMAall, (12.2)
where
Qur(t) = Aa(0) exp (— iw,1) (12.3)
and
Aua(t) = (€oV)? ey exp (ik.r). (12.4)
Here the wave vector k and the angular frequency w, are related by wy, =
kc, and V, the volume under consideration, may be made arbitrarily large. In
addition, for each value of k there are two independent polarization vectors
€, and these are distinguished by the subscript A(= 1, 2). The two possi-
bilities for €,, are orthogonal to each other and because of the Coulomb
gauge condition they are both orthogonal to k:

nn Kn’ = bans 4 ,-K = 0. (12.5)

Quantum Field Theory C27

The energy of the field is then given by the classical Hamiltonian (Equation
6.83):
H = & wx (Gindiar + VrVin: (12.6)
Although this Hamiltonian is expressed in terms of pairs of variables,
Qua and qyy, they do not form conjugate pairs and are not appropriate for
quantization. This situation was remedied in Section 6.7, where the new real
variables:
Ow = Wat dm; Pay st OW OE) (12.7)
were introduced, the inverse relation being:

Fux = (WxOKA t iP r)/2W,- (12.8)

There it was shown that P,, may be regarded as the momentum conjugate
to Q;, and that in terms of these new variables the field energy is:

ae (Pia + WEQKa)- (12.9)

Consequently, we consider the theory based on quantization of the conju-
gate pairs, P,, and Q,. The final justification for this policy is, of course,
that the resulting theory works.
To get from the classical theory to the quantum theory the Q,, and Py
are regarded as operators satisfying commutation relations analogous to
Equations 12.1. Operators corresponding to different values of k or A are
independent of each other, so that the appropriate commutation relations are:

[Paras Ox'n'] = — hb ya dyy'5

(12.10)
[Pras Pern] = (Qua, Qxr'] = 0.
The Hamiltonian (Equation 12.9) is now to be regarded as an operator and
is to be used in the Schrédinger equation HW = ihaW/0dt.
For stationary states the Schrdédinger equation reduces to HW = EW and
this may be solved using the separation of variables method with the result
that:
Ey ie SareeEx; ; po aitAL Va (12d )
where £;,, and W,, are the solutions of the separated equation:

HinVarn = Era (12.12)

with
Hun = 4(Pkra + wkQka)- (12.13)
We note that after quantization the field can still be regarded as a collection
of radiation oscillators, since Equation 12.13 is just the Hamiltonian for a
228 Advanced Molecular Quantum Mechanics

one-dimensional harmonic oscillator. The solution of Equation 12.12 is con-

sidered in the next section, but before then other aspects of quantization are
considered, since the operator forms of the vector potential and the electric
and magnetic fields are needed later.
Although q,, and its complex conjugate gx, cannot be used directly in
the quantization procedure, they are now to be regarded as operators defined
by the operator form of Equation 12.8. Using this definition their commu-
tation relations may easily be determined from Equations 12.10:

[da> qn] = (A/20,)8 yadyn’;

(12.14)
[dur Wx'n'] = [aka Wea] =*O,

We may now investigate the validity of quantizing the vector potential

(Equation 12.2) by interpreting q,, and gx, as time-independent operators.
This procedure must be consistent with the rest of the quantization scheme
and to confirm this the Hamiltonian must now be derived from the quantized
potential.
To do this the operator forms of the electric and magnetic fields are
needed. The magnetic field operator is readily shown to be:

B= V,A= Ry i(durxk, Aun — Vark , Ada) (22,15)

but a problem arises for the electric field operator, since it is given by
E=— dA/dt and q,y, and qj, are both time-independent operators. The
origin of this difficulty is that we are using the Schrodinger picture in which
operators are time independent and the wave functions evolve with time.
The alternative formalism involves time-dependent operators and time-inde-
pendent wave functions. This is the Heisenberg picture, but it may be made
to coincide with the Schrodinger picture at t= 0. Heisenberg’s equation
of motion (Equation 1.24) shows that:

dgya/dt = (i/h)[H, dual = 1 OL Ens (12.16)

a result that may easily be obtained from Equations 12.8 to 12.10; this is
analogous to the classical result and may be used in the Schrédinger picture
at time ¢ = 0. The electric field operator is then:

E = —dA/0t = & ic(Qur Ara — Ger Ai): (12.17)

Equations 12.15 and 12.17 for the electric and magnetic field operators
may now be used to determine the Hamiltonian from Equation 6.46:

H = 4€0Sf(c?B?
+ E*)dr. (12.18)
Quantum Field Theory 229

The manipulations involved are the same as those in the classical derivation of
Section 6.7 except that it is now important to preserve the order of gq, and
dx» since they do not commute. However, this was anticipated in the classi-
cal treatment so that Equation 6.83 is also valid quantum-mechanically:

H = & winder + derTin): (12.19)

When this Hamiltonian is expressed in terms of the operators Py, and Oy,
using Equation 12.8, we recover:

eae 3(Pka + we Oka), (12.20)

so that the quantization procedure outlined is self-consistent.
The classical derivation of the field momentum in Chapter 6 also needs no
modification after quantization, since the order of q,, and qj, was pre-
served; in addition Equations 12.14 now justify the policy used there of
ignoring the order of, for example, Qxx and q,'y’. Thus:

G = % Ga, (12.21)
where

Gir = k(Gidna + GkATRD)

= }(k/c4)(Pha + wh Qian)
(ion yee (12.22)
Finally, we may show that Maxwell’s equations for a free field may be
recovered after quantization. From Equations 12.15 to 12.17 the first pair
are obtained:
V-Ba—s0: Vie — (0B/d1), (12.23)

but these are merely a consequence of the definition of the electric and
magnetic fields in terms of the potentials. The divergence of the electric field
is easily shown to vanish, since in the gauge chosen ¢ vanishes and A satisfies
the Coulomb condition (V.A = 0), so that:
V.E = —a(V.A)/dt = 0. (12.24)
The remaining equation is more difficult to obtain. It is first noted that,
from Equations 12.16 and 12.17:

(OE/dt) = wi (erAra + TirAnn): (12.25)

while the curl of Equation 12.15 gives:

VB = K?(qr Anan + erAkD) (12.26)

230 Advanced Molecular Quantum Mechanics

where
V i(k, Ana) = k(V.A,))— (K.V)A,, = — ik? Ayn (12.27)

has been used. Since w, = ck, comparison of Equations 12.25 and 12.26
shows that:
VRB c ?(dE/df), (12.28)

which is the required equation.

12.2 Solution of the one-dimensional harmonic oscillator equation

For simplicity the subscripts in the one-dimensional harmonic oscillator

equation may be omitted. Equation 12.12 is then Hy = Ey and the Hamil-
tonian is given by Equation 12.20 as H = 4(P? + w?Q’). The solutions of this
equation could be obtained by replacing P by — ih(0/0Q) and solving the
resulting differential equation for wy in the usual manner. However, for the
electromagnetic field it is not possible to give a simple physical meaning to
the operator Q or to wave functions that are functions of Q. As it happens
interpretations of Q and wW(Q) are not needed and we choose to solve the
harmonic oscillator equation in a different way. Furthermore, this alternative
approach is much more instructive in the present context.
Now that quantization has been accomplished the operators q and q* may
again be used. However, it is more convenient to define the dimensionless
operator:
a = (2w/h)?q, (12.29)
for which the commutation relations are:

dag ic ae ali [aa] =1a7.0° |) =.0: (12.30)

as may be seen by reference to Equations 12.14. The Hamiltonian now be-
comes:
KH = thw(a*a + aa*), (12.31)
or using Equations 12.30:

H = hoa*a+4) = hu(N +3). (12.32)

The new operator N = aa is of particular interest, since unlike a and a*
it is Hermitian. If n is an eigenvalue of N and the corresponding normalized
eigenfunction is |m), we may write:

N\n) = n\n) (12.33)

and, since N is Hermitian, m must be real. From Equation 12.32 it is seen that
Quantum Field Theory ZS

the |n) are also eigenfunctions of H€ with eigenvalues hux(n + 4).

To investigate the properties of N and its eigenvalues, the commutation
relations of N with a and a™ are first determined using Equations 12.30:

[a, N] laaal = [42a" la =n:

(12.34]
[a*, N]"'= [a*, a*a) =a" [a*, 2] = — a":
Now, operating on |) with the operator Na* and using these commutation
relations:
Na*|n) = (a*N +a*)|n) = a*(N+1)|n) = (nt 1)a*|n), (12.35)
so that a*|n) is also an eigenfunction of N and, since the corresponding
eigenvalue is (7 + 1), it must be proportional to |n + 1):

a*|n) = e,|n + 1), (12.36)

where c, is a constant. Similarly, it may be shown that a|n) is an eigen-

function of NVwith eigenvalue (n — 1):

Na|n) = (aN—a)|n) = a(N—1)|n) = (2—1)aln), (12.37)

so that:
a|ln) = c|n—1). (12.38)

The proportionality constants c, and c_ have been introduced because the

eigenfunctions a*|n) and a|n) are not necessarily normalized, but they may
be evaluated by considering:

fe:|2-= Gilas*[n) = nIN+1ln) = n+ 1 (12.39)

and
lc_|? = (nla*a|n) = (n|N|n) = n. (12.40)
The phases of c, and c_ cannot be determined and it is normal practice to
1 i
take them to be zero, so that c, and c_ are (n + 1)? and n?, respectively:

a*|n) = (nt+1)i[n+1);— aln) = n?|n—1). (12.41)

The next stage in this development is to find the possible values of n.
From Equation 12.40 it may be seen that n must be positive or zero, since
|c_|? is obtained by taking a wave function, multiplying it by its complex
conjugate and integrating over the appropriate space. If m were non-integer it
would be possible to apply the operator a repeatedly to |n) until an eigen-
function with a negative value of m was obtained. However, it is possible for
n to be an integer, since Equations 12.41 show that this inconsistency does
not then arise:

aln) = n2|n—1);...; all) = 10); al0) = 0; (12.42)

2a7 Advanced Molecular Quantum Mechanics

further application of a can only give zero. We conclude that n is a positive

integer or Zero.
The eigenvalues of the Hamiltonian (Equation 12.32) are thus:

E = hon +3); A) OF al A (12.43)

a result in accord with that of the more traditional approach. In addition, we
may note that the |”) are also eigenfunctions of the momentum operator,
which from Equations 12.22 and 12.29 is:

G = $hk(a*a + aa*)
= nk(N + 4), (12.44)
so that:
G|n) = Ak(n + 4)|n). (12.45)
The eigenvectors |m) may all be expressed in terms of |0), since repeated
use of Equations 12.41 shows that:

In) = (n!)2(@*)"10). (12.46)

For our purposes in the present chapter there is no need to enquire more
closely into the nature of |). If, however, the one-dimensional harmonic
oscillator wave functions are required in terms of the coordinate Q, this
approach may easily be extended. Provided |0) is known as a function of Q,
other eigenfunctions may be generated using Equation 12.46 with a™ re-
placed by the operator (wo/2h)? [OQ — (h/w)d/dQ]. The explicit form of |0)is
readily obtained from the equation a|0) = 0, which is equivalent to the dif-
ferential equation:
[9/8Q
+ (w/h)Q]|0) = 0. (12.47)
The normalized solution of Equation 12.47 is just:

|0) = (w/hm)# exp (— wO?/2h) (12.48)

and this too is in agreement with the results of other approaches.

12.3. Creation and annihilation operators

In the previous section the energy of the eigenfunction |n) for an individual
radiation oscillator was seen to be fiw(n + 4). The quantum number n may
be regarded as the number of quanta of energy Aw in the oscillator in ad-
dition to the zero-point energy of 4hw. For this reason n is known as the
occupation number and, since it is the eigenvalue of N, this operator is
called the number operator.
Quantum Field Theory 233

Now a™* operating on |) increases the number of quanta by one to give,

within a numerical factor, the eigenfunction |n + 1). Consequently, a™ is
called a creation operator. In the same way a is an annihilation operator, since
it reduces the occupation number by one. In this terminology it is the quanta
of energy that are created or annihilated.
So far we have confined ourselves to just one radiation oscillator, although
in reality there are an infinite number each characterized by a wave vector k
and a polarization \. For every oscillator we can define a creation and an-
nihilation operator and these are distinguished by the subscripts k and X.
From Equations 12.14 and 12.29 these may be seen to satisfy the commu-
tation relations:

[aa> OR'n’] = Sick’ An’ 5 Cae Ax'n'] = [axn, axa’) = 0. (12.49)

In addition, a number operator Nj, and a Hamiltonian #,,, may be defined

for each oscillator and the corresponding eigenfunctions may be designated
by |p).
The electromagnetic field as a whole is described (Equations 12.11) by an
eigenfunction which is the product of the eigenfunctions for the individual
radiation oscillators:

Jt [gn = [ry licgag? +> - |r; --

= ORE Myr Ok} Nk dp Abs (12.50)

An operator specific to one wave vector and polarization only acts on the
corresponding part of the eigenfunction, so that, for example, use of Ny;
tells us how many quanta of type k;, A; are present:

Nx jn;| ro Mag dg> ++» Maprp- >

= Mm a,l Mr Mery +++ 9 Mjrp >>?» (12251)

Thus the total energy of the field is given by:

E= Ro hur, (nyn + 4), (12-52)

as would be expected.
In specifying a state of the field it is only necessary to mention those
quantum numbers 1, that differ from zero, although all the possibilities for
k and A must be remembered in performing a summation such as in Equation
12.52 because of the zero-point energy. Thus, if there are no quanta present,
Lp Degas ee", On ap oe may be abbreviated to |0) and this is known as
the vacuum state.
234 Advanced Molecular Quantum Mechanics

Any state of the radiation field may be constructed from the vacuum
state by using the appropriate creation operators. For a state of the field with
just one quantum of type k, X:

1a) = a4, 10), (12-53)

while for two quanta of the same type:

[2un) = 272(a%,)?10), (12.54)

as may be seen by reference to Equation 12.46. For two quanta of different
types the factor 27? does not occur:

lex: 1K'n” = a ayn’ | 0) = Ae'y' A 10). (12:55)

Finally, we note that, since all creation operators commute with one another
(Equations 12.49), it does not matter in which order the quanta are created.

12.4 Photons

In the last section it was seen that the energy of an electromagnetic field is
the sum of the quanta of energy associated with the individual radiation
oscillators. These quanta may be identified with particles or photons and it
is the purpose of this section to show that this identification is consistent
with photons being massless particles which obey Bose-Einstein statistics.
If we consider just one photon with wave vector k and polarization A, we
know that it has energy how, and, from Equation 12.45, momentum hk.
Now Equation 4.41 relates the energy & and momentum p of a particle:

E = c(mc?
+ p?)2, (12.56)
so that the mass of the photon is given by:

m = (E*—c*p*)i/c? = h(w?
— c?k?)i/c?. (12.57)
Since w, = ck, Equation 12.57 shows that the photon has no mass.
In this formalism there can be any number of photons in the same state,
that is having a particular wave vector, polarization and energy. In addition, in
creating photons from the vacuum state the order of creation is immaterial
so that the state of the radiation field is symmetric with respect to inter-
change of any two photons; this fact depends on the commutation of all
creation operators. Particles with these properties satisfy Bose-Einstein stat-
istics, so that photons are bosons. These remarks apply to any type of particle
or quantum of energy, for which the creation operators all commute; for
Quantum Field Theory 235

example vibrational quanta in a molecular oscillator may be thought of as

vibrational ‘particles’ or vibrons. Now Bose-Einstein statistics are obeyed by
particles with zero or integer spin, so that we might enquire whether the
photon possesses a spin. In fact it may be shown to have spin one and this
property is related to the fact that two polarizations are possible for a given
wave vector (see bibliography).
Thus the classical wave theory for electromagnetic fields becomes a par-
ticle theory on quantization. If there are a great number of photons, the
occupation numbers 1, become very large and may be regarded as con-
tinuous variables; this is the classical limit. This situation is to be contrasted
with classical particle theory, which on quantization becomes a wave theory.
Both radiation and matter demonstrate a wave-particle duality, but the roles
are reversed.

12.5 Zero-point energy and vacuum fluctuations

Up to now a discussion of the zero-point energy of the radiation field has

been omitted. For the vacuum state there are no photons, but according to
Equation 12.52 there is an energy Rt shu, associated with the radiation

field and this energy is infinite, since the sum is over all possible wave vectors.
From Equation 12.45 the field momentum of the vacuum state may be
seen to be PA $hk, but no problem arises here, since for every wave vector k
.

in the summation there is also a wave vector — k, so that the field momentum
vanishes.
Nevertheless, it is disturbing that the vacuum state has an infinite energy.
This problem may conveniently be ignored by taking the energy of the
vacuum state to be the origin of the energy scale. This may be achieved
formally by starting with the classical expression:

H = kAY wWederdna (12.58)

which on quantization gives:

H = % hora: (12.59)

In addition, we must impose the rule that in products, such as those in-
volved in Equation 12.18, creation operators must always be placed on the
left of annihilation operators, since, if they are not, it is possible to have a
creation operator acting directly on the vacuum state and this leads to in-
finite quantities. This restriction may seem a little contrived, but a self-
consistent theory can be developed; in effect the zero-point energy of the
236 Advanced Molecular Quantum Mechanics

radiation field is consistently ignored. However, this situation is not very

satisfying and we consider the zero-point energy more closely.
The analogy between a radiation oscillator and a molecular vibration has
been emphasized on a number of occasions. A vibration also has a zero-point
energy and this may be regarded as a manifestation of Heisenberg’s uncer-
tainty principle, which may be stated as:

(AA)(AB) > {<[A, B] )/2i\; (12.60)

the product of the uncertainties in two observables is greater than or equal to
a quantity which depends on the expectation value of the commutator of
their operators. For a vibration the vibrational coordinate and the vibrational
momentum do not commute, so that they cannot both be zero and there
must always be some energy associated with the vibration.
In the case of a radiation field it is instructive to consider the commu-
tators of the number operator Vy, (= a, 44, ) with the electric and magnetic
field operators (Equations 12.17 and 12.15). Using Equations 12.29 and 12.49
these may readily be obtained:

[Mas E] = — i(fier,/2)? (ar Ara + a A*);

(12.61)
[Meax, B] = — i(h/2e,)? (aerk, Ana + ak, AX)-
Neither of these commutators vanish, so that if the number of photons is
approximately fixed E and B are uncertain. For the vacuum state there are
no photons at all so that the electric and magnetic fields are very uncertain.
The expectation values of the operators E and B in the vacuum state are
both zero:
{O|E|O) = (O|B/O) = 0, (12.62)
since these operators are linear in creation and annihilation operators. How-
ever, the expectation values of E” and B? do not vanish, since they both
involve the operator a,,@%,, for which the expectation value in the vacuum
state is unity. For example it may readily be shown that:

k,A

R24 hur, /2€ V, (12.63)

where Equation 12.4 has been used. The sum (Equation 12.63) is infinite
even if the volume V is allowed to become infinite, since the number density
(Equation 6.74) for k is proportional to V. Similarly we may obtain:

(0|B?|0) = PA hu,/2c7egV (12.64)

Quantum Field Theory 237

and by substituting this and Equation 12.63 into Equation 12.18 and inte-
grating over the volume V the zero-point energy, D 4/w,, may be recovered.
Thus, in the vacuum state the electric and magnetic fields fluctuate wildly,
although their expectation values vanish. These are the so-called vacuum
fluctuations. However, it is not at present clear whether the vacuum fluc-
tuations and the zero-point energy are one and the same thing. As we
have already remarked the latter may be formally removed from the theory,
but the former may not be avoided so easily. Indeed, the vacuum fluctuations
do lead to observable effects. For example, they have already been invoked
(Section 11.9) in a crude explanation of the major part of the Lamb shift.
However, further discussion of this topic is not possible here, since treating
the electron as a point charge leads to infinities and the circumvention of
this difficulty involves the more sophisticated techniques of mass and charge
renormalization.

12.6 Fermions and second quantization

The theory that has been developed in this chapter is appropriate to photons,
but it may readily be adapted to describe other particles that satisfy Bose-
Einstein statistics. It is based essentially on the commutation relations (Equa-
tion 12.30) for the creation and annihilation operators:

ifg =A; [aa] = {a*,a*])= 0: (12.65)

These relations lead automatically to the possibility of having any number of
particles in the same state and, in addition, they are responsible for many-
particle states being symmetric with respect to interchange of two particles;
these are the properties characteristic of bosons.
However, this formalism is not adequate to describe fermions and in par-
ticular electrons. These obey Fermi-Dirac statistics, which require that there
be no more than one particle in a given state and that many-particle states be
antisymmetric with respect to interchange of two particles. Thus, the Pauli
exclusion principle must somehow be incorporated into the theory. To con-
clude this chapter the way this may be done is described, but a detailed
discussion would be out of place here.
Creation and annihilation operators are again used, but these are given the
new symbols b* and b,, respectively, to distinguish them from the boson
operators; the label r indicates the one-particle state to which the operators
apply. However, these operators are required to satisfy the anticommutation
relations:

[D3 b,*],= Ores [b,, Bale = fees: bole = 0, (12.66)

238 Advanced Molecular Quantum Mechanics

where
[A, B], = AB + BA. (12.67)

As for bosons we may define a vacuum state |0) in which there are no
particles present. A single-particle state may then be constructed by oper-
ating on the vacuum state with a creation operator:

[1-) = by |). (12.68)

Further application of a creation operator gives a two-particle state:

b*b¥ (0) = bFH1,)°= 115, 1p) (12.69)

where r * s. However, it is not possible to have two particles in the same state,
since from Equation 12.66:

brbs|0) = 4[b-, b-],10) = 0. (12.70)

In addition, the anticommutation relations dictate that the two-particle state
(Equation 12.69) is antisymmetric with respect to interchange of the par-
ticles:
[1p dpi=eb SbEO 2b She Oe lp (2 -71))
This is just what is required by the Pauli exclusion principle.
By analogy with the number operator for bosons we may define the new
operator:
N, = byb, (12.72)
and it may easily be confirmed that this is a fermion number operator:

N= O)-=) Dab.
| Os. 0:
N,|1,) II N,bs|0) = b*b,b*|0)

be (i= Br b;.)0) = obs Oa ai1,); (12.73)

The operator N, is said to be idempotent, since its square is equal to itself:

No = bib D*b,. = h(i bop he =p bee re (12.74)

where we have used the fact (Equations 12.66) that b,b, must vanish. Thus,
Equation 12.74 shows that:

N?—N, = NAN, —1) = 0, (12.75)

so that the eigenvalues of N, are zero or one, that is, a state r may be un-
occupied or occupied by just one fermion; this is consistent with our earlier
conclusions.
Quantum Field Theory 239

The creation and annihilation operators, a* and a, for bosons may be

expressed in terms of a variable Q and its conjugate momentum P, and indeed
the theory was developed via P and Q. However, the fermion operators b*
and b, have been introduced directly, but this is necessary, since they cannot
be associated with a variable and its conjugate momentum. This situation is
a reflection on the fact that there is no classically measurable field corre-
sponding to quantized fermions.
The use of creation and annihilation operators to describe fermions, and
in particular electrons, implies that they are to be treated as particles. Yet
the usual quantum theory uses a wave description for fermions and we might
enquire how the formalism developed above may be employed. For bosons
the classical wave theory becomes a particle theory on quantization. In the
same way the quantum-mechanical wave function for a fermion may be
treated as a field variable and quantization then gives a particle theory for
which creation and annihilation operators are appropriate. This procedure is
known as second quantization for obvious reasons. Its advantage is that it
provides a convenient way of describing many-particle systems and in par-
ticular it may be used to describe situations in which the number of particles
is not conserved. For example, in Section 9.5 a crude model was given for
the origin of the electron’s g factor anomaly. This involved the creation of a
virtual electron-positron pair and in the Dirac theory of Chapter 8 this is
described as the excitation of an electron from the filled negative energy
states; in this theory the number of electrons is conserved, but at the ex-
pense of having to describe the electron by a many-particle theory. Using
second quantization the necessity for particle number conservation disappears.
In addition, the theory based on second quantization may be used to prove
the exclusion principle of Pauli. Needless to say these topics cannot be con-
sidered further.

Bibliography

Quantization of the electromagnetic field

Grandy: Chapter 9.
Hameka: Section 6-2.
Sakurai: pages 20-36.
Ziman, J. M. (1969), Elements of Advanced Quantum Theory, Cambridge
University Press, Cambridge: pages 1-5 describe the solution of the har-
monic oscillator equation using creation and annihilation operators.

Photon spin
Grandy: pages 138-140.
240 Advanced Molecular Quantum Mechanics

Sakurai: pages 30-31.

Vacuum fluctuations
Grandy: pages 141-143.
Sakurai: pages 32-36.

Second quantization
Sakurai: pages 28-29 and 143-156.
Schiff, L. I. (1968), Quantum Mechanics, McGraw-Hill, New York: pages 498-
508.
 CHAPTER THIRTEEN

The Interaction of Radiation and Matter

The usual approach to the absorption and emission of radiation by matter

is to use the semiclassical theory in which, although the matter is treated
quantum-mechanically, the radiation is described classically. For the more
elementary applications it is possible to obtain the correct results using this
theory, although it is often necessary to use indirect arguments. In addition,
there are phenomena which cannot be described by the semiclassical theory.
However, the quantum theory of radiation that was developed in the
previous chapter provides an appropriate basis for describing the interaction
of radiation with quantized matter. Not only does the resulting theory avoid
the problems of the semiclassical approach, but it is more generally applicable
and provides a conceptually simpler picture of the processes involved. The
semiclassical theory is given in many of the more elementary texts and for
this reason it is not detailed here, although a comparison of the two
approaches is given in Section 13.5.
The Hamiltonian for electromagnetic radiation in free space was found in
the previous chapter. In the first section of this chapter the interaction
Hamiltonian is considered, but before this may be done we must decide
what sort of Hamiltonian to use for the description of the quantized matter.
In much of what follows the interaction of the radiation with a single elec-
tron is discussed, but, since the results are to be generalized to a molecule, it
is appropriate to use a non-relativistic approximation to the Hamiltonian.
Thus, the theory to be developed is not a relativistic one. However, many of
the same principles apply if the Dirac Hamiltonian for an electron is used
and the differences are pointed out at the appropriate place in the develop-
ment. As it happens for the phenomena considered here the results are
identical, to the accuracy employed.
241
242 Advanced Molecular Quantum Mechanics

13.1. The interaction Hamiltonian

To illustrate the principles involved the interaction of radiation with a single

electron is considered, but we may anticipate the generalization of the results
to molecules by assuming that the electron has discrete energy levels. The
Hamiltonian for the system may be written as the sum of three parts, one
for the field, one for the electron and one for the interaction between the
two:
H = Hp
t+He + Hint. C132)

The quantized field Hamiltonian Hy was obtained in the last chapter and, as
has already been remarked, the non-relativistic approximation is used for the
electron’s Hamiltonian H,. The interaction Hamiltonian H;,,; must now be
discussed.
The non-relativistic approximation to the Hamiltonian of an electron in
an electromagnetic field was derived in Chapter 8. This is a semiclassical
Hamiltonian in the sense that the radiation field was treated classically. From
this Hamiltonian (Equation 8.142) we may select those terms involving the
electromagnetic potentials to obtain the semiclassical interaction Hamiltonian:

Hint = —eb+ (e/2m)(p.A + A.p) + (e?/2m)A? + (eh/m)(s.B), (13.2)

where the symbols have the usual meaning and the term 7*/2m has been ex-
panded (Section 7.1). There are, of course, smaller terms that could be
added to this, but they are negligible as far as the time-dependent processes
considered in this chapter are concerned. When it is recalled that the gauge
chosen for the potentials is such that ¢ and V.A vanish at every point in
space, Equation 13.2 reduces to:

Hine = (e/m)(A.p)+ (e*/2m)A? + (eh/m)s.B). (13.3)

The semiclassical interaction Hamiltonian (Equation 13.3) may be put in
a fully quantized form merely by interpreting the vector potential A as the
linear combination of annihilation and creation operators obtained in the
last chapter:
A = & (fi/2wx)? GerAnr + afAtr)s (13.4)
where the Ay, are given by Equation 12.4. The magnetic field B is now also
an operator and is given by:

B= % i(/2w)? Giak , Aga —aityk , At). (13.5)

The Interaction of Radiation and Matter 243

In describing the interaction of molecules with electromagnetic radiation

the interaction Hamiltonian is relatively small and will be taken as a pertur-
bation in the subsequent treatment. The total Hamiltonian (Equation 13.1)
may thus be rewritten as Ho + Hj,;. The unperturbed Hamiltonian Ho is the
sum of the field and electron Hamiltonians and because it contains no inter-
action terms its eigenfunctions may be written as a product of the eigen-
functions of Hs and HH. taken separately. In talking about the state of the
system we then mean a combined state of electron and photons.
The perturbation #;,; contains creation and annihilation operators, so
that it connects states with differing numbers of photons. The terms in-
volving A.p and s.B in Equation 13.3 are linear in these operators so that
they have matrix elements between states differing by one photon; it should
already be apparent that these terms are involved in single-photon absorption
and emission phenomena. The remaining term in Equation 13.3 is propor-
tional to A? and is quadratic in creation and annihilation operators so that it
connects states differing by zero or two photons. It will be seen that, al-
though this term can be important in scattering processes, where the number
of photons is conserved, it is not involved in two-photon absorption or
emission and it is the A.p term taken to second order that is responsible.
The interaction Hamiltonian (Equation 13.3) was obtained from the non-
relativistic approximation to the Dirac Hamiltonian for the electron and we
might inquire what would happen if the Dirac Hamiltonian itself was used. In
this case the perturbation representing the interaction of the electron with
quantized radiation is:
Hint = eca.A. (13.6)

This differs from Equation 13.3 in that there is no term in A” so that it is not
obvious that the two interaction Hamiltonians can ever lead to the same
results for some phenomena. This is a reflection of the fact that the Dirac
theory of the electron is really a many-particle theory, since it is necessary
to assume that all the negative energy states are occupied by electrons
(Section 8.6). For a correct treatment this has to be taken into account,
since the Dirac operator « connects positive and negative energy states. How-
ever, we will not go into the details, since for the generalization to molecules
it is more convenient to use Equation 13.3 as the interaction Hamiltonian.

13.2 Time-dependent perturbation theory

The interaction Hamiltonian is a relatively small perturbation on molecular

systems and the phenomena to be discussed in this chapter are described well
244 Advanced Molecular Quantum Mechanics

by time-dependent perturbation theory. This section is devoted to deriving

those results of this theory that are needed later. This material could have
been relegated to an appendix, but, although the first-order theory is prob-
ably familiar, it is necessary to go to second order to describe some of the
processes discussed later. The theory developed is quite general, but it should
be remembered that for our purposes a state describes a system consisting of
radiation as well as a molecule.
Approximate solutions are required for the time-dependent Schrodinger
equation:
HW(t) = ih(dWv(t)/dt), (13.7)

where H =H y+ V and it is assumed that the eigenfunctions of Ho are

known:
Hon a EnWn- (13.8)

The perturbation V is a time-independent operator, since the Schrodinger

picture is being used, but nevertheless it can cause the state of the system
to change with time.
The solutions W(t) of Equation 13.7 may be written as a linear combin-
ation of the eigenfunctions W, of Ho:

W(t) = Yen(t)Un exp (—iE,t/h). (13.9)

The coefficients c,,(t) may be determined by substituting this into Equation

13.7, reorganizing, multiplying on the left by Wz exp ((E,t/A) and integrating
over all space. The result is:

C(t) = —(i/h) ~ VencCal(Qexp: {Ge — En. (13.10)

where ¢;, is the derivative of c, with respect to time and Vz, is the time-
independent quantity:

Ven = ‘k|Vin) = fweVWpdr. (13.11)

Let us consider transitions from an initial state i. For the boundary con-
ditions it is assumed that initially, that is at t = — ©, only state 7 is populated,
so that:
Cyl ae Ont (13212)
An approximate solution of the coupled differential equations (13.10) may
now be obtained by substituting this condition and integrating:

crt) = Sei — G/M)Vii S-_exp [iE — Eit'/Aldt’. (13.13)

The Interaction of Radiation and Matter 245

The definite integral in Equation 13.13 cannot be evaluated at its lower

limit. This could be avoided by taking our initial condition to be Cn(0) = 8p;
instead of Equation 13.12 so that the integration would be from 0 to t
(assumed positive). However, this condition corresponds to a sudden and
artificial turning on of the perturbation at tf = 0. Not only is this physically
unreasonable, but also it introduces spurious terms in second order. To cir-
cumvent these difficulties the initial condition (Equation 13.12) is retained,
but a mathematical trick is used. The time-independent perturbation Vis re-
placed by Vexp (nt), where 7 is real and positive. This has the effect of
turning the perturbation on gradually as ¢ increases from —°. The integration
may then be performed and the original problem recovered by taking the
limit as 7 goes to zero at the end of the calculation.
With the replacement of V by V exp (nt) Equation 13.10 becomes:

Ce(t) = — G/h) Vienen(t) exp [Ex —En)t/h + nt], (13.14)

the approximate solution being:

C(t) = dni + Ves exp [i(Ex — E;)t/h + nt] (Ei

— Ep + ihn). (13.15)
Although this is only an approximate solution, it encourages us to enquire if
the exact solution of Equation 13.14 may be obtained by merely replacing
the V;,; by some new quantities R;,;:

Cr(t) = Sei t+Rei exp [i(Ex — E;)t/h + nt] /(Ei

— Ex + ihn). (13.16)
If this proves successful the identity of the Ry; has then to be determined.
Substitution of Equation 13.16 into Equation 13.14 followed by multi-
plication throughout by exp [—i(E, — £;)t/h— nt] results in the equation:

Rei = Vei + © VienRni exp (nt)/(E; — En + ifn). (13.17)

n

This may be solved iteratively for R;; and so long as the perturbation is small
compared with (£; — £,,) the resulting series converges rapidly:

Rei = Vai + Z VienVni exp (nt)/(Ei — En + iin)

Va Vain Va OD 20)Ey — Eat IE Em Fin) ee. =;
n,m
(13.18)

although these R,; are time-dependent this dependence is removed when 7 is

eventually allowed to become zero. Thus, Equation 13.16 is a solution of
Equation 13.14, the R;; being given by the series 13.18.
In practice we are interested in the transition from the initial state 7 to a
246 Advanced Molecular Quantum Mechanics

final state f, The probability of the system being in state f at time ¢ is just
|c,(t)|? and from Equation 13.16 this is given by:

le, (t)|? = IR Fi ‘ieexp (2nt)/ [(E; att Ey ae hn? | E (13.19)

The transition rate w,; from i to fis obtained by taking the time derivative of
this probability:

Wri II dic, (t)|?/dt

= 2 exp (2nt)|Reil? {n/[(E; — Ep)’ + hn? J}. (13.20)

The limit as n tends to zero may now be taken. To do this we note that
the term in curly parentheses in Equation 13.20 is related to a representation
of a Dirac delta function:

Lt, (nlm?
+1?)]= 8(2). (13.21)
If x *O the limit tends to zero, while for x =O the limit is infinite. In
addition, it may easily be shown that:

f= [nie? + 1?) dx = 1. (13.22)

Thus, Equation 13.20 may be replaced by:

Wei = (2n/h)|Rei|?5(E7
— Ej); (13.23)
here, use has been made of the fact (Equation 2.88) that 5(cx) =c 18(x),
where c is a constant. In this connection we might note that 5(E — Ej) has
the dimensions (energy)', so that wy; has the correct dimensions of (time)?.
Equation 13.23 is to be used in conjunction with Equation 13.18, which in
the limit as n tends to zero becomes:

Rri = Veit » VinVnil(Ei — En)

the Ry; are called the reaction matrix elements.

Since it involves a Dirac delta function, Equation 13.23 is an operator
equation and an appropriate integration must be carried out; the details de-
pend on the problem being discussed and are given explicitly for the appli-
cations considered later. However, it is apparent from Equation 13.23 that
energy is conserved in a transition.
There are difficulties in this approach to time-dependent perturbation
theory. For example, in the expansion 13.24 the terms for n =i and m=i
The Interaction of Radiation and Matter 247

must be omitted from the summations if infinities are to be avoided. Other

deficiencies of this theory are discussed in Section 13.8.

13.3. Matrix elements of the interaction Hamiltonian

In this section the matrix elements of the individual terms in the perturbation
(Equation 13.3) are considered, since they are needed in the application of
Equations 13.23 and 13.24. For convenience, it is assumed that only one
type of photon is present, the generalization to all types being made later.
The state of the unperturbed system is then given by an eigenfunction of
Ho (= He + Hf):
|A, nxn) = |A)|ng,), (13.25)
where |A) and |.) are eigenfunctions of He and Hf, respectively.
The perturbation (e/m)(A.p) is linear in creation and annihilation oper-
ators, so that its only non-zero matrix elements are of the type:

(B, Mux — 1|(e/m)(A.p)|A, nen)

= (e/m)(hinyy|20, Veo)? xr 4B exp (ik.r)p|A) (13.26)

and

(B, Nyx + 1|(e/m)(A.p)|A, nea?

= (e/m)(F(nya + 1)/2weVEo)? &ka-<Bl exp (—ik.r)p|A); (13.27)

in evaluating the radiation part of these matrix elements use has been made
of Equations 13.4, 12.4 and 12.41. The first of these represents the absorp-
tion of a photon by the electron accompanied by a transition from state A
to state B, while the second corresponds to an emission process.
The matrix elements (B| exp (+ik.r)p|A) between electron states are en-
countered in the semiclassical theory. Since the wavelength k~’ of the radi-
ation is normally very large compared with molecular dimensions, it is usual
to make the long wavelength approximation. This involves taking the origin
of the electron coordinate r to be in the molecule and expanding the expo-
nential as a power series in k.r. This expansion parameter is very small com-
pared with one so that only the first term in the expansion need be retained,
that is, exp (tik.r) is replaced by unity. The problem now reduces to that
of evaluating (B|p|A), but this may be expressed in a more convenient form
by taking |A) and IB) to be eigenfunctions of the approximate electronic
Hamiltonian:

He spingel (e); (13.28)

248 Advanced Molecular Quantum Mechanics

where U(r) is a potential function. We then have:

[H.,1] = — (him), (13.29)

so that
(‘B\p|A) = (im/h)‘B\| [He, r] |A)

= (im(Eg — E,)/he)‘Bler|A>

= im(Eg — E,4)Pgalhe. (13.30)

With these approximations the matrix element, Equation 13.26, becomes:

(B, My — 11(e/m)(A.p)|A, 24a)

= i(ny/2hw, Veo)? (Eg — Ea) &erPpa; (13.31)

with a similar expression for 13.27.
For simplicity only one electron has been considered so far and, in doing
this, summations and electron and nuclear subscripts have been avoided. How-
ever, the preceding development is readily extended to molecules. The per-
turbation (e/m)(A.p) must be summed over all electrons and nuclei, but the
same results are obtained provided |A) and |B) are now eigenfunctions of the
molecular Hamiltonian and Pg, becomes the matrix element of the mol-
ecular electric dipole moment between |A) and |B). Consequently these
matrix elements are responsible for the so-called electric dipole transitions in
molecules.
There are situations where Pg, vanishes and it is necessary to go to the
second term in the expansion of exp (+ik.r) to obtain non-zero matrix
elements:
(B| exp (+ ik.r)p|A) = (B|p|A)+i(Bl(k.r)plA4)+.... (13.32)
The additional matrix element may be evaluated by splitting it in two:

(B\(k.r)p|A) = 4[<B| (k.r)p + (k.p)r|A)

+ (B| (kK.r)p — (k.p)r|A)]. (13733)

By noting that for the electronic Hamiltonian (Equation 13.28):

[He, 7373] = — Ghlm)@ir; + 7p;) ESee tard Mme oi2

the first part of Equation 13.33 may be shown to be:

3(B\(k.r)p + (k.p)rl4) = (im(Eg — E4)/2he?)(B|T|A).k, (13.35)

where the tensor T has components Tj = e?7r,r;. On substitution into
Equations 13.26 or 13.27 the scalar product of Equation 13.35 with e,,
The Interaction of Radiation and Matter 249

must be taken and, since €,,.k vanishes (Equations 12.5), the results are un-
altered if the scalar —e7r?/3 is added to each of the diagonal elements of T.
This gives a new tensor QO with elements:

Oy = e7(7, 7; — dSyr?/3). (13.36)

When we generalize to a molecule, Q,; is just the contribution of the electron
to the molecular electric quadrupole moment. In this way matrix elements
corresponding to electric quadrupole transitions are obtained.
To evaluate the second part of Equation 13.33 we again recall that we are
interested in its scalar product with €,,, so that we may use:

(K.r)(ein-P) — (Kp)(Ena-t) = (Ky e4a)-(, p)s (13.37)

this relation also depends on the fact that €,,.k = 0. Thus:

4 €.(B| (k.r)p — (k.p)r|

A)

= (m/e)(Ky &4,).(B|(e/2m)(r, p)|A). (13.38)

Now (e/2m)(r, p) is the orbital magnetic moment of the electron and ref-
erence to Equation 13.5 shows that (kK,€,,) is related to the magnetic field
so that the matrix element (Equation 13.38) gives rise to magnetic dipole
transitions.
So far only the first term in the interaction Hamiltonian (Equation 13.3)
has been considered. The last term (e%/m)(s.B) also leads to magnetic dipole
trdnsitions. For illustration the matrix element corresponding to absorption
is quoted:

(B, ny — 1|(eh/m\s.B)|A)
= i(Feyn/204, Veo)? (Ky € nx) (BI (€h/m)s| A), (13.39)
where the long wavelength approximation has been used. The similarity to
the other magnetic dipole matrix element (Equation 13.38) is easily seen.
The electric quadrupole and magnetic dipole contributions to the matrix
elements of the interaction Hamiltonian are in general smaller than the
electric dipole contribution by a factor of order kr, where k is the reciprocal
of the wavelength of the radiation and r is of molecular dimensions. They are
important when the electric dipole matrix element Pg, vanishes or when
special techniques are employed; for example, it is the magnetic dipole con-
tribution that is usually involved in magnetic resonance. In the rest of this
chapter only the electric dipole contributions are considered, since we are
interested in principles rather than details, but in practice the other contri-
butions may be dealt with in much the same way.
250 Advanced Molecular Quantum Mechanics

There is one term in the interaction Hamiltonian that has yet to be con-
sidered, this being (e?/2m)A?. Since it is quadratic in creation and annihil-
ation operators, it can connect states differing by zero or two photons and in
general two types of photon must be considered. Now (e7/2m)A? is a much
smaller perturbation than (e/m)(A.p), so that the long wavelength approxi-
mation may again be made and only the first term in the expansions of the
exponentials need be retained. The resulting matrix element connecting states
with the same total number of photons is:

(B, Nk Ny Ny’ x! a | (e?/2m)A?|A, NX> Nyx’)

= [ent ,(nyy + 1)2(eqr-x’n’)/2mwew?-Veo] (BIA). (13.40)

Since the eigenfunctions of H, are orthogonal to one another, this must
vanish unless A and B are the same electron state. At the end of the last
section it was seen that energy is conserved in transitions so that the import-
ant matrix elements of the type 13.40 are those in which wy, and w,’ are
equal. This matrix element then corresponds to Rayleigh scattering in which
the incident and scattered photons have the same energy and the electron
state is unaltered. The matrix elements of (e?/2m)A’ between states differing
by two photons, that is those connecting |A, nya, n,',’) with |B, ny, +1,
ny’x' + 1), are also proportional to (B|A) and are unimportant, since energy
conservation is not possible if A = B.

13.4 Absorption and emission

The absorption of a single photon by a molecule in state A to give the

molecule in state B may be represented by the equation:

A+ 7>B, (13.41)
where y is a photon. Initially just one type of photon is considered, but
eventually the summation over all types must be made. Thus, the initial
state 7 is |A, n,) and the final state fis |B, ny, — 1).
The transition rate is given by Equation 13.23:

Maa = (27/h)|Ryi\?5(E¢ — E;). (13.42)

Since it is a single-photon process that is under discussion, only the leading

term V;; in the expansion 13.24 for Ry; is relevant; the other terms represent
many-photon processes, which are discussed later. This matrix element V Fi
has been considered already and the major contribution to it is the electric
dipole contribution given in Equation 13.31. Thus, Equation 13.42 becomes:
The Interaction of Radiation and Matter 251

Wri = (IA? Veo)(M4,/

We) Exr- Ppa) (Ep —Ea)’5(Ep — E4 — fivoy)
yn, &x( &,-Pg4)5(Eg — LE, — hw,),
= (n/Veo) (13.43)

where fw,, E,4 and Ep are the energy of the photon and the molecular
states A and B respectively.
So far just one type of photon has been considered and, in addition,
Equation 13.43 is an operator equation. It is now necessary to sum over
the photon polarization \ and all the possible wave vectors k. To do this it is
expedient to replace the summation over k by an integration over w and the
solid angle Q. At the same time a number density p(w) must be introduced
and from Equation 6.75 this is just Vw?/(27c)°. Thus we make the replace-
ment:

i f (Voo?/(21¢)?)dwd&. (13.44)

Before performing the integration it is convenient to express n;, in

Equation 13.43 in terms of the radiation intensity /(w), which is defined so
that [(w)dw is the energy per unit volume of radiation with angular fre-
quency between w and w+ dw; it is assumed here that all polarizations and
orientations of k are equally likely but the details may be modified to deal
with other cases. Now each photon contributes an energy hw/V to the in-
tensity, so that:
I(w)dw = nyy(hw/V)(Voo2?/(21c)*)81dw. (13.45)
Here the number density p(w) has again been used and the factor 87 arises
from the sum over the two possible polarizations for each k and integration
over the orientations of k. On rearrangement Equation 13.45 gives:

My = Mw)n?c3/hw®. (13.46)
Using 13.44 and Equation 13.46 the transition rate (Equation 13.43)
now becomes:

Wah = 2 J ((w)/8e€oh)( €g).Ppay oer =f = hw)dwdQ. (13.47)

The sum over \ and the angular integration is performed first, the relevant
part of Equation 13.47 being:

Z f (#,-Ppa) do. (13.48)

The situation is illustrated in Fig. 13.1; x, is the angle between Pg, and
€,, and the angular integration is over 0 and ¢. The expression 13.48
2352 Advanced Molecular Quantum Mechanics

reduces to:
x f [Pzal7 cos? x, dQ = |Pgal?fsin?0dQ, (13.49)

where the trigonometric relations:

cos X; = sin @ cos ¢; cos X, = sind sing (13.50)

have been used. The angular integral is now readily evaluated and 13.48
becomes (877/3)|P3,|*, so that the transition rate is:

wri = S (tI(w)|Ppal?/3 €0h)6(Eg — Ea — hw)dw. (13.51)

Fig. 13.1. The relative orientations of Pg, and €,,.

Finally, the integration over w must be performed and this is readily

accomplished using Equations 2.82 and 2.88:

Wi ll= T(w)|Pp4l?/3€ oh?

= BpeaKw), (13.52)

where Bg, is the Einstein coefficient for absorption and, because energy
is conserved in the transition:

w = (Fg —E,)/h. (13.53)

The corresponding emission process, that is:

CA, (13.54)
The Interaction of Radiation and Matter 255

may be treated in very much the same way. If just one type of photon is con-
sidered the initial and final states are |B, m,,) and |A, ny, + 1) respectively
and from Equation 13.27 the transition rate for emission is:

Wai = (n/Veo)\(ny, + 1)a4.(€xa-Pap)5(E4 — Ez + hex). (13.55)

When this is compared with the analogous equation (13.43) for absorption >

it is noticed that for emission the transition rate may be split into two parts.
The first is proportional to m,, and hence to the intensity of the radiation.
This gives rise to stimulated emission, since it depends on radiation being
present. The second part is independent of n,, and has no counterpart in ab-
sorption. It is responsible for spontaneous emission, since it does not vanish
when there is no radiation present initially. These two parts are considered
separately.
The stimulated emission term is similar to the absorption transition rate
(Equation 13.43) and may be processed in the same way. Reference to
Equation 13.52 shows that after the inclusion of all types of photons the
stimulated emission rate is given by:

Wri TI (w2)|P.4p17/3€oh”

= By pl(w), (13.56)
where w again satisfies the energy conservation condition (Equation 13.53).
The Einstein coefficient for stimulated emission B, <p is precisely the same
as that for absorption Bg.,. It is emphasized that this emission only occurs
if there is radiation of the appropriate frequency already present and this is
why it is said to be stimulated (or induced).
When 7, vanishes, Equation 13.55 reduces to the transition rate for
spontaneous emission. This equation is for one type of photon only and must
be summed over k and i. The sum over k may be replaced by an integral
using the prescription 13.44 and the sum over \ and the angular integration
may be performed as for the absorption case, since all directions of emission
and polarization are equally likely. This gives:

Wri iy(w?|Pp4|7/31c7% €o)5(Ea — Ex + hw)dw

\I w?|Ppal?/3nc%
€oh
eA ey (13:57)

where w is given by Equation 13.53 and A,~-z is the Einstein coefficient of

spontaneous emission. This emission occurs whether radiation of the appro-
priate energy is present or not.
254 Advanced Molecular Quantum Mechanics

13.5 Comparison of the semiclassical and quantized theories

In the semiclassical theory the radiation is described classically and in par-

ticular the vector potential is a function of space coordinates. The radiation
can influence a molecule but it cannot be influenced by the molecule in
return. When the molecule makes a radiative transition the vector potential
is not affected. This theory works whenever the radiation is sufficiently in-
tense that the appearance or disappearance of a single photon has a negligible
effect on the intensity.
The details of the use of the semiclassical theory to describe the absorp-
tion and emission of radiation is given in many texts. The absorption process
may be accounted for quite readily with this theory and with some difficulty
so can stimulated emission. However, the semiclassical theory is incapable of
describing spontaneous emission, since classically A vanishes when there is
no radiation and the interaction Hamiltonian disappears.
The way in which this problem is surmounted is to use Planck’s radiation
law, which may be derived from statistical mechanics, to relate the Einstein
coefficients of stimulated and spontaneous emission. In addition, this ap-
proach shows that the Einstein coefficients of absorption and stimulated
emission are equal, so that in practice only the absorption process needs to
be considered in the semiclassical theory. The results are the same as those
obtained in the previous section.
If the quantized theory of radiation is used the absorption and emission
rates are obtained directly and there is no need to invoke Planck’s radiation
law. In addition, both stimulated and spontaneous emission arise in the same
way. Even when there is no radiation present a molecule may interact with
the radiation vacuum state and this may be attributed to the presence of the
vacuum fluctuations (Section 12.5).
Not surprisingly the quantized theory may be used to derive Planck’s
radiation law. We consider a collection of molecules and a radiation field
that can exchange energy by the emission and absorption of photons:

At+y +B. (13.58)

When thermal equilibrium is established the ratio of the numbers of mole-
cules in states A and B is given by the Boltzmann law:

NalNp = qo) (hw/kT), (13.59)

where hw = Ez — Ey and k is the Boltzmann constant. Now, N4 and Nz are

also related by the equilibrium condition that N4/N, is equal to the ratio of
the emission rate to the absorption rate. When it is remembered that both
The Interaction of Radiation and Matter Pie

stimulated and spontaneous emission are possible, use of Equations 13.52,

13.56 and 13.57 shows that:

NalNg = 1+ (w?h/n7I(w)c?). (13.60)

Combination of Equations 13.59 and 13.60 now gives:

Kw) = wh/n?c3 [exp (hw/kT)— 1], (13.61)

or in terms of the frequency p rather than the angular frequency w:

I(v) = 8rhv?/c3 [exp (hv/kT)— 1]. (13.62)

Although only one frequency of radiation has been considered this equa-
tion can immediately be extended to all frequencies if it is assumed that the
radiation field is surrounded by black walls consisting of molecules capable
of absorbing and emitting photons of all energies. Equation 13.62 is just
Planck’s radiation law, which gives the energy density of radiation in equi-
librium with its surroundings at a temperature T.
Finally, it may be remarked that the quantized theory provides a more
appealing physical picture for the interaction of radiation with matter, since
photons are absorbed and emitted and energy is conserved. Indeed these
processes may conveniently be described by diagrams. In Fig. 13.2 time in-
creases from the bottom to the top of the page, the wavy lines represent pho-
tons and the straight lines molecular states; although there is a resemblance,
these are strictly not Feynman diagrams. In the present instance these dia-
grams are trivial, but similar diagrams can be very useful in discussing many-
photon processes, since they provide a convenient way of keeping track of all
the terms in the expansion 13.24 of the reaction matrix element.
8B A ie

y
ce A e
B

A+Y—B8 B-—Aty
absorption emission

Fig. 13.2. Diagrams describing absorption and emission.

256 Advanced Molecular Quantum Mechanics

13.6 Multi-photon processes

Two-photon absorption has been observed in microwave and radio-frequency

spectra and also, with the advent of intense laser sources, in the optical
spectra of, for example, organic crystals. Although only the case of two-
photon absorption is briefly considered here, the principles may readily be
extended to emission and multi-photon processes.
In practice the two photons absorbed are usually of the same frequency,
but we discuss the general case:

At+tyty-B. (13.63)

Thus, the initial state is |A, m,,,/x’,’) and the final state is |B, m,, —1,
ny/x’ — 1). The transition rate wy; is given by Equation 13.23, so that a non-
zero reaction matrix element R;; is needed. The first term in the expansion
13.24 of Ry; is V;;, but this vanishes. In the first place the perturbation
(e/m)(A.p) only connects states differing by one photon. Secondly, although
(e?/2m)A? connects states differing by two photons its matrix elements are
proportional to (B|A), which is zero in this case; this depends on the use of
the long wavelength approximation, but higher terms in the expansion of
exp (ik.r) make negligible contributions.
For a non-zero R;; it is necessary to go to the second term in its expansion
and this is just:
z Vin Vil (Ei — En). (13.64)

Only the perturbation (e/m)(A.p) makes a significant contribution and then

only if the state n is |J, yy, My,’ — 1) or |Z, ny — 1, ny’n'), Where J is any
state of the molecular system. Use of Equation 13.31 then gives:

Ryi = — (Matyn |x)? hVeoy |E (Ep — E(Er — Ea) X

[(€ica-Par(€x’r’
Pra )/(Ea — Ey + hwy’)

+ (epn'-Pa)(€xa-Pra)/(Eq — Ey + hw,)). (13.65)

This may now be substituted in Equation 13.23 to give the transition rate.
As for one-photon processes generalization to all types of photons must be
made, but this may be accomplished in a similar manner. The details are not
given here, but it may be noted that the presence of the Dirac delta function
in Equation 13.23 ensures that the transition rate vanishes unless energy is
conserved in the overall process:
The Interaction of Radiation and Matter PT]

A few words are appropriate about the molecular states J, which are called
intermediate or virtual states. They are definite molecular states and as such
they are eigenfunctions of the molecular Hamiltonian. However, these states
cannot be observed in the two-photon process. Over the entire process energy
is conserved, but it is not necessarily conserved while the molecule is in an
intermediate state. The reason for this is that the lifetime of an intermediate
state is so short that Heisenberg’s uncertainty principle allows there to be some
uncertainty in its energy. Strictly speaking, the intermediate states include
continuum states and an appropriate integral over these states should be
added to the sum over the discrete states in Equation 13.65; however, they
are usually unimportant because the corresponding energy denominators are
very large.

B B

(a) T ig
sf Y

A 1 A
Y Y

A ye A

(b) a

B 1

(c)
/
if
16 A B

Fig. 13.3. Diagrams describing (a) two-photon absorption: AL ae Par 7 >B,

(b) two-photon emission: B>A+y+tv7, (c) negligible two-photon absorp-
tion and emission processes.
258 Advanced Molecular Quantum Mechanics

The two-photon absorption (Equation 13.63) may be described by the

diagrams given in Fig. 13.3(a). There is a diagram for each of the two per-
turbation terms in Equation 13.65; in one case the photon y is absorbed
first and in the other it is y’. In Fig. 13.3(b) the corresponding diagrams
for the two-photon emission process:

BoAt+yty (13.67)

are given. Finally, the negligible absorption and emission processes due to the
perturbation (e?/m)A? are described by the diagrams in Fig. 13.3(c); in this
case there are no intermediate states, since the operator A? connects states
differing by two photons and in principle can contribute to the first term
V;; in the expansion 13.24 of Rj.

13.7 The scattering of photons by molecules

In the two-photon processes discussed in the last section both photons are
either absorbed or emitted. However, it is possible for one photon to be
absorbed and one to be emitted:

A+ y>Bty; (13.68)
this process is referred to as scattering. If y and y’ both have the same energy
and A = B we have Rayleigh scattering, while the more general phenomenon
where y and y’ are of different energy and 4 ¥ B is known as Raman scat-
tering.

B uf B
y ‘

je

i rf
” A
(a) (b) (c)

Fig. 13.4. Diagrams describing photon scattering: A + y > B+ 7.

The general process 13.68 may be described using diagrams as in

Fig. 13.4. In (a) the photon y is absorbed to give an intermediate state J
which subsequently emits the photon y’. However, there is no reason why
y should not be emitted before y is absorbed and this possibility is illus-
trated in (b). The first-order process in which absorption and emission occur
The Interaction of Radiation and Matter 259

simultaneously is shown in (c); this is due to the perturbation (e?/2m)A? and

is only important for Rayleigh scattering for which A = B.
We again consider a single bound electron, but as before the generalization
to a molecule may be made without difficulty. The initial state for the
scattering process may be taken as |A, 24 ,”,',') and the final state as
|B, Mx — 1, ny’y’ + 1). The matrix element of the perturbation (e?/2m)A? be-
tween these two states is given by Equation 13.40. The second-order
contribution of (e/m)(A.p) to the reaction matrix element is given by
13.64 and in this case the relevant states n are J, my, —1, my’,’) and
W, Myx, My’y’ + 1); the first occurs in diagram (a) in Fig. 13.4 and the second
in diagram (b). Thus, the matrix element R;; is given by:

Rei = [Maryn + 1)/co,,co4'] ? (2hVEo)! Xx

{(e7hi7/m)(€xn-€x'rx’)5aB — 2 (Eg — E;)(E1 — Ea) X

[(€xa-Pad(€x’a’-Pra)/(Ea — £7 — wy’)
+ (€x/n'-Pap)(€xa-Pra)/(Ea — Ey + heo,)) }. (13.69)
This may now be used to calculate the transition rate, but the details of any
further development depend on the experimental situation under consider-
ation. Indeed, Equation 13.69 and similar expressions provide a starting point
for a discussion of many phenomena such as optical rotation and related
effects as well as Rayleigh and Raman scattering. However, except for a few
more general remarks, this topic is not pursued further.
If the energy of the incident and scattered photons is much larger than
the binding energy of the electrons, only the first term in the curly paren-
theses of Equation 13.69 is important. The scattering is largely due to the
process depicted in (c) of Fig. 13.4 and is insensitive to the binding of the
electron; this is the situation exploited in X-ray diffraction, for example.
When the photon energy is small the resulting Rayleigh and Raman scattering
is usually described in terms of molecular polarizability and this section is
concluded with a demonstration that Equation 13.69 is related to a polariz-
ability matrix element for the specific case of Rayleigh scattering, in which
A= Band wy, = wx.
The initial step is to rewrite the first term in Equation 13.69 in a similar
form to those involving intermediate states. This is done by noting that,
because of the commutation relations of p and r:
IAC €,-€4'r’) = (ema-r)(€n’r’-P)— (€x'n’-P)Exa-r)
LD [Al egy-r ll €'n'-plA?
I
+ (Alex'y-pIDV |e -t1A)], (13.70)
260 Advanced Molecular Quantum Mechanics

where the completeness of the intermediate states J has been used. Use of
Equation 13.30 now shows that:

(7h? /m)(€xn-€x'r’) = a — Ey) [(€xx-Par(€x'n’

Pra)
+ (€4'\'-Par(€xa-Pra)], (13779
where P,, is the matrix element of er between A and /. The expression in
Equation 13.69 which is enclosed in curly parentheses now becomes:

hw 2 (E;— Eq)[(€xx-Pap(€x'n'-Pra)/(Ex —E, +hw)

— (€4/n'-Pap(€qa-Pra)/(Er — Ea — hu)). (13.72)

Since Aw is assumed to be much smaller than (£;—£,) the terms

(E, —E, +hw)' may be expanded as power series in hus/(£,; — E.4) and only
the linear terms need be retained. Thus, Equation 13.72 is approximated by:

D hoo[(€x-Panle Pea) — (€y/9'-Pap(€xa-Pra)I

I
ai 2 (hw) [(exr-Panle w’'n'-Pra) + (€x'a?-Par(€xa-Pra)] (Er — Ea). (13.73)

Now the first term vanishes, since it is proportional to the matrix element
(Al [(€x,-1), (€x/n'-4)] |A), so that the reaction matrix element R,; is finally
given by:

Rr = — [Myalny'n’ + 1)]?(fivo/2 Veo) X

zs[Ce xr-Pan(€x'a’-Pra) + (€x’a’-Par(€xa-Pra)]/(Er — Ea). (13.74)

Although Equation 13.74 has been derived for a single bound electron
R,; has the same form for a molecule and can be rewritten as:
Rei = — [eaten + 1)]? (eo/2Veo) €4,-4A lelA)-€,'n’, (13.75)
where a@ is the molecular polarizability tensor. This concludes our demon-
stration that for low energy photons the Rayleigh scattering may be described
in terms of the molecular polarizability.

13.8 Line widths and resonance fluorescence

It has already been mentioned that the time-dependent perturbation theory

in Section 13.2 has deficiencies. One of these is that the theory leads to
transitions that are infinitely sharp, although in practice spectral lines have
a finite line width. Of course, there are a number of causes for line broadening.
The Interaction of Radiation and Matter 261

For example, in high resolution gas phase studies the Doppler effect and
pressure broadening are important. However, even if these contributions are
eliminated there is a residual line width, known as the natural line width,
which cannot be removed.
Another difficulty is that the reaction matrix element (Equation 13.69)
for photon scattering involves the denominator (E, — E,;+ hw), where hw
is the energy of an incident photon. If Aw is equal to (EL;— £4) for an inter-
mediate state /, then Ry;, and hence the transition rate wy;, both become
infinite. This does not, of course, occur in practice, although in the region
where hww=E,;—E, the scattering probability is observed to go through
a sharp maximum. This phenomenon is called resonance fluorescence.
Both the natural line width and resonance fluorescence may be attributed
to the fact that excited states have finite lifetimes and that this is not ac-
counted for in the theory of Section 13.2. Heisenberg’s uncertainty prin-
ciple, which is stated in Equation 12.60, shows that the lifetime 7 of a state
and the uncertainty in its energy are related by:

T(AE) > h/2, (13.76)

where we have used the fact that the energy operator is if(0/0r); thus, AE is
of the order of f/r. For the ground state of a molecule in the absence of
radiation the lifetime is infinite and the energy is well defined. However,
excited states have finite lifetimes, since photon emission is always possible
even if there is no radiation present. In general the average lifetime of a state
is the reciprocal of the sum of the transition rates to all other states. Conse-
quently, the energy of an excited state cannot be definite and the energy level
is smeared out.
This uncertainty in the energies of excited states means that all spectral
lines are broadened, since transitions always involve excited molecular states
even if, as in the case of Rayleigh scattering by a molecule in its ground state,
the excited states involved are intermediate states. The uncertainty in the
energies of states was not accounted for in the theory of Section 13.2, since
in obtaining Equation 13.10 it was assumed that the states are eigenfunctions
of Hy and that their energies are constant and independent of time. As a
result the differential equation 13.10 allows for a build up of a particular
state by transitions from other states, but it does not account for the de-
pletion of that state by transitions from it. This possibility can be allowed
for phenomenologically by adding an extra term c;,(t)exp(—t/2T,) to
Equation 13.10 for ¢,(t). Inclusion of this term then leads to finite line
widths for transitions.
262 Advanced Molecular Quan tum Mechanics

These are qualitative considerations, but the results arise naturally in more
advanced theories. Here, we confine ourselves to an unsophisticated demon-
stration that finite line widths are predicted by quantitative treatments. To
do this we consider a system consisting of just two states, a and b. Corre-
sponding to Equation 13.10 there is then a pair of coupled differential
equations:
Ca = — (i/h)Vaycy exp [i(Ea — Ep)t/h]
(13.77)
Cy = — A)Voala exp [iE, — Eq)t/h] }.
To simplify the subsequent development it is assumed that at time t=0
only state a is populated, so that

c,(0) = 1; c,(0) = 0. (13.78)

In Section 13.2 initial conditions of this type were deliberately avoided, since
they give spurious terms in second order, but here only the first-order results
are considered.
The qualitative discussion earlier suggests that state a will decay as exp
(— t/Tq), so that c, will decrease as exp (— t/27,), since the probability of the
system being in state a is given by |c,|?. Consequently, the trial solution:

¢,(1) = exo 127) (13.79)

is investigated. By substituting this in the second of Equations 13.77 a differ-

ential equation in c, alone is obtained and the solution of this using the
initial conditions (Equations 13.78) gives:

Gp = Voa (exp [i(F, rs Eth ae 27,1 ae 1V/(E, —E,, ao ih/2r7,). (13.80)

The first of Equations 13.77 may now be used with Equations 13.79 and
13.80 to determine 7;':

Ta’ = (2i/h)| Vaol?(1 — exp [i(Eq — Ey)t/h + t/274])/(Eq — Ey — ih/2T9),

(13.81)
or neglecting terms in 7, on the right-hand side of this equation:

Ta = (2i/h)| Vapl?(1 — exp [i(Eq — Ey)t/h])/(Ea— Ep); (13.82)

the justification for this neglect is that Ar,’ is very much smaller than
(E, i Ey).
Now 7;' is expected to be time independent and indeed this has been
assumed in obtaining Equation 13.82. Consequently, the limit of Equation
13.82 is taken as f>© and to avoid oscillations we employ the same trick
The Interaction of Radiation and Matter 263

as before (Section 13.2) and insert an artificial damping factor, which is

later made to vanish. Abbreviating (E, — E,)/h to x, we have:

Lt ld — exp (ix))/x] — ify exp (ixt)dt

Il = a ne exp (ixt — nt)dt
ll Lt +iny!

Lt, [xI(x? + 1?) —in|(x? + 1?)]

1/x — ind(x), (13.83)

where the representation (Equation 13.21) of a Dirac delta function has

been used. Thus, Equation 13.82 becomes:

Ta' = (2i/h)| Vopl"/(Ea — Eo) + (2n/h)| Vanl?5(Ea — Ep). (13.84)

Reference to Equations 13.9 and 13.79 shows that the imaginary part of
T,' leads to an energy shift. It is a term like this that is responsible for the
Lamb shift (Section 11.9), the two levels being an electron plus the vacuum
state and the electron plus a photon. The electron emits a photon which it
subsequently absorbs and, since the emission is due to the electron inter-
acting with the vacuum state, the vacuum fluctuations may be considered to
be responsible for the Lamb shift.
The real part of 7,’ (Equation 13.84) is just the rate of transition (Equation
13.23) from state a to state b, so that 7, is the lifetime of state a in the
two-level system under consideration. This result is in agreement with the
qualitative arguments given earlier.
We are now in a position to consider the line shape associated with the
transition a to b. At t=© the transition is certain to have taken place and
from Equation 13.80:
Cp(©°) = — Vogl(Ba—Ep — il 21,): (13.85)

The transition probability is then:

le,(©)I? = | Vool?/ (a — Ee)? + 7/472]. (13.86)

The important thing to note is that this is not proportional to a Dirac delta
function, but is an ordinary function of the energy difference (E, — Ey), so
that the spectral line associated with the transition is not infinitely sharp.
If the transition from a to b involves the absorption or emission of a
photon of energy Aw by a molecule in state A to give the molecular state
B, we can write:
E,—E, = Eq, —Ep thw = h(wot w). (13.87)
264 Advanced Molecular Quantum Mechanics

The transition probability (Equation 13.86) is then a function of the photon

energy and is proportional to:

[(w — wo)? + 1/473)". (13.88)

Thus, the spectral line corresponding to the transition has the Lorentz shape.
It is centred on w= Ww, and has a width at half height of 7,’, so that the
natural line width is just equal to the transition rate from a to b.
Although only a two-state system has been considered, the extension to
more complicated systems yields analogous results, the width of a line being
the total transition rate to all other states. These considerations also provide
an explanation for resonance fluorescence, which was mentioned earlier and
which occurs in scattering processes when the incident photon energy is the
same as the energy difference between the initial state of the molecule and
one of the intermediate states. A more sophisticated theory is needed, since
scattering involves second-order processes, but the result is that the reaction
matrix element (Equation 13.69) is modified by the replacement of the
denominator (FE, — E; + hu) by (FE, — E; + hw, — ih/27;) as in the sim-
pler example considered here. As a consequence the transition rate does not
become infinite when E; — FE, = hw,, although it does have a maximum in
agreement with experiment.

Bibliography

The interaction of radiation and matter

Grandy: pages 201-211.
Hameka: the interaction Hamiltonian is discussed in Section 6-3, absorption
and emission in Chapter 7 and scattering in Chapters 11 and 12.
Sakurai: pages 36-57.
Wallace, R. (1966), ‘Diagrammatic perturbation theory of multiphoton tran-
sitions’, Molec. Phys., 11, 457.

Time-dependent perturbation theory

Grandy: Appendix C.
Hameka: Chapter 5.

Line widths and resonance fluorescence

Heitler, W. (1954), The Quantum Theory of Radiation, Clarendon Press,
Oxford: pages 181-189.
Sakurai: pages 53-57 describe the phenomenological approach, which is
justified in pages 65-68.
APPENDIX A

Units

This book employs the “Systéme International d’Unités’ (SI). (It is also known
as the (rationalized) MKSA system, since four of the base units employed are
the metre, kilogram, second and ampere.) A discussion of the advantages of
using this system is given in Section 5.1. Here a brief summary is given, with
particular reference to those units used in this text. For the details of these and
other units, reference should be made to the bibliography.

A.1 SI units

There are three types of SI units: base, supplementary and derived.

(a) The seven base units are regarded as being dimensionally independent:

Physical quantity Dimension

Symbol

length metre
mass kilogram
time second
electric current ampere
thermodynamic temperature kelvin
luminous intensity candela
amount of substance mole

265
266 Advanced Molecular Quantum Mechanics

(b) There are two supplementary units:

Physical quantity
Name Symbol

plane angle radian rad

solid angle steradian sr

(c) Derived units are employed for all other physical quantities. They are said
to be coherent, since they are obtained by multiplying and dividing the base
units without introducing any numerical factors whatsoever. Some of these
have special names and symbols:

Physical quantity

energy joule
force newton
pressure pascal ia}

power watt
electric charge coulomb
electric potential
volt
difference
electric resistance | ohm
electric
farad
capacitance
magnetic flux weber (ey
inductance henry
magnetic flux
tesla Ae!
@hesbinc)
<a)
Lap
tes
eect
=a)
density
frequency hertz xN

There are other derived units which have no special names or symbols. Many
of these are obvious, such as that for density (kg m~*), and only the pertinent
electromagnetic units are given here. For completeness electric charge, electric
potential and magnetic flux density are included, although their units have
special names.
Units 267

Symbol for
Physical quantity SI unit Dimensions

electric charge (e
| w I =
electric field strength E Vm!
electric displacement D Cm?
permittivity €(D = €E) Fm! wn Ey N
ile
tles
is | w | _
electric potential ¢ Vv Nn

\
electric charge density p Che w

electric dipole moment Cm

magnetic field strength H Am! ty
i
magnetic flux density B it
permeability u(B = uH) Hm!
vector potential A Tm te
wee(See
islere
[Se
Me
ins
fel
TS
LSS
Ee
Ne

electric current density j Am?

magnetic dipole moment i Gan Ga
Ee
OSS
RAAAARAAAD
ALA

(d) Decimal multiples (in steps of 10%) of SI units are indicated by prefixes:

Multiple Symbol | Multiple Symbol

me
milli
micro M
nano G
pico T
femto
atto

A.2 Conversion from the mixed (Gaussian) CGS system to the SI system

(a) The conversion of equations expressed in the mixed CGS system to the
corresponding SI equations only poses problems if electromagnetic quantities
are involved. For the situations considered in this book the conversion may
be accomplished using the following table, the quantity in the CGS column
being replaced by the expression in the SI column. Before the conversion all
quantities must be expressed in mixed CGS units and after the conversion all
must be in SI units.
268 Advanced Molecular Quantum Mechanics

Dimensions in the mixed

Physical quantity

electric charge a per q(4m€o)

electric field strength Ly? 77} E(47€,)!”
1/2 p(4m€9)
electric potential
magnetic flux density B(Uo/4m) 1?
vector potential A(Uo/47) 1?
Bohr magneton Lp (Mol 4m)?

This table must not be used to provide numerical conversion factors for units,
since powers of 10 must be introduced to allow for the change from centi-
metres and grams to metres and kilograms; this topic is considered below.
(b) Conversion factors for units are given in the following table:

Z : : Conversion factor | Definition

Physical quantity | Name of unit Gist units) se wait

energy erg rg |
calorie* : 4.2)
wave number (cm7') 1.986001 0. 29
electron volt 1.6022 X10 @ 1.6022 X
(ev)t Oy SA
force dyne 10° 10°°N
electric charge+ e€.$.u. (4765) 10272 33334C10 Ee
electric field e.s.u. cm7! cro? 2.998 X 10?
strength+ Vm"!
electric dipole debye (108 (Ameo)? 107 72” 3:334x%10-8
moment €.s.u.cm)
magnetic flux gauss (G) (el 4a) O10"
density

* Only an approximate conversion factor is given, since there are various

types of calories.
+ The electron volt is the product of the charge on the proton and the unit V.
+ Note that the practical CGS units for electric charge and electric potential
are the coulomb and the volt, respectively, and that these are SI units.

A.3. Recommended values of fundamental constants

The uncertainties in these values (one standard-deviation) are indicated by the

numbers in parentheses; for example, the uncertainty in the velocity of light
in a vacuum is 0.0000010 X 108 ms! or 1.0X 10?ms"1.
Units 269

Fundamental Constant

velocity of light in a Cc 2.9979250(10) X 108 ms"!

vacuum
permeability of a vacuum} Uo 4m X 10°7H m! (exact)
permittivity of a vacuum | €9 = tp!c2 8.8541853(58) X 10°'*F m"!
fine structure constant Q = Uge*c/2h Te2OTSoL CLL elon
a} 137.03602(21)
charge of a proton e 1.6021917(70) X 10°1°C
Planck constant h 6.626196(50) X 10 “Js
h=h/2n 1.0545919(80) X 10 **Js
unified atomic mass my, = mq('7C)/12 | 1.660531(11) X 10°?7kg
constant
rest mass of electron Me 9.109558(54) X 10 *!kg
rest mass of proton Mp 1.672614(11) X 10° 2’kg
Mp/Me 1836.109(11)
Rydberg constant Rn. = Mamee*c?/8h>| 1.09737312(11) X 107m"!
Bohr radius Ag = h?/TUoc? mee? |5.2917715(81) X 10! m
Bohr magneton Mp = eh/2me 9.274096(65) X 10“ JT"!
nuclear magneton Un =(melmp)ug | 5.050951(50) X 10°?7JT™!
free electron g factor 2.002319315(7)
Boltzmann constant 1.380622(59) X 10. JK™
Avogadro constant 6.022169(40) X 107? mol!
gravitational constant 6.6732(31) X 10° '!Nm?kg?

Bibliography
The Symbols Committee of the Royal Society (1971), Quantities, Units and
Symbols, The Royal Society, London.
McGlaschan, M. L. (1971), Physico-Chemical Quantities and Units (second
edition), The Royal Institute of Chemistry (London), Monographs for
Teachers, number 15.
Taylor, B. N., Parker, W. H., and Langenberg, D. N. (1969), ‘Determination
of e/h, using macroscopic quantum phase coherence in superconductors.
Implications for quantum electrodynamics and the fundamental physical
constants’, Rev. Mod. Phys., 41, 375: with the exception of the electron
g factor (see Section 9.5) the values of the fundamental constants quoted
here are taken from this reference.
Coulson, C. A. (1958), Electricity, Oliver and Boyd, Edinburgh: Chapter 14.
APPENDIX B

Vector Relations in Three Dimensions

General relations. The scalar ¢ and the components of the vectors A, B,....
are all assumed to commute with one another; V is the vector operator with
components (0/dr;).

A(B,C) = B(C,A) = C(A,B),

A, (B,C) = (A.C)B— (A.B)C,
(A,B).(C,D) = (A.C)(B.D)— (A.D\(B.C),
V.(@A) = (V¢).A + 6(V.A),
VA(GA) = (VO),A + (VA),
V(A.B) = (B.V)A + (A.V)B + B,(V, A) + Aq (V,B),
V.(A,B) = (V,A).B— A.(V,B),
V,(A,B) = A(V.B)— (A.V)B + (B.V)A— (V.A)b,
V,\(V4) = 0,
V.(V,A) = 0,
V,(V,A) = V(V.A)— VA.
Special relations involving the position vector r; 6(r) is the Dirac delta function
(see Section 2.13).

Vir = 3,

270
Vector Relations in Three Dimensions 271

Vi/r) = —+/r’,
Vi/r) = —V.@/r?) = — 475(9),

Vi(r;/r*) = (47/3)65 5(r) = 5 /r? — 3r;r,/r°.

The derivation of other relations is often facilitated by the use of €;;, (see
Chapter 2). The following sum rules may be useful:

€kEimn = On Rn On Obs

€yrEyn = 25en>
€ik Eijk = (os
APPENDIX C

General Bibliography

The following references are cited a number of times in this book. They are
referred to by the authors’ names in the bibliographies at the ends of the
chapters.

Bethe,H. A., and Salpeter, E. E. (1957), Quantum Mechanics of One- and

Two-Electron Atoms, Springer-Verlag, Berlin.
Feynman, R. P., Leighton, R. B., and Sands, M. (1964), The Feynman Lec-
tures in Physics, Addison-Wesley, Reading, Mass.
Foldy, L. L. (1962). ‘Relativistic wave equations’, Pure Appl. Physics (D.R.
Bates, editor. Academic Press, New York), 10 (part 3), 1.
Grandy, W.T., Jr. (1970), Introduction to Electrodynamics and Radiation,
Academic Press, New York.
Hameka,H. F. (1965), Advanced Quantum Chemistry, Addison-Wesley,
Reading, Mass.
Landau, L. D., and Lifschitz, E.M. (1962), The Classical Theory of Fields,
Pergamon Press, Oxford.
Rose, M. E. (1961), Relativistic Electron Theory, Wiley, New York.
Sakurai, J.J. (1967), Advanced Quantum Mechanics, Addison-Wesley, Reading,
Mass.

Die
Indexes
 =

_<
#7 4S
,¢ e264 x

Ly =
*s

=. _
- =
~ < SS
S ~
SeeSn a
as =

— =
=~ _
—=

ec oe tarot: 4 a at
—— . ne Ca S pits - ne ii Soa wh ee , r .

i ~

~ My
~

ny = Pe OF P| e= Sede
sai
is

sis Sf adh, TS
oe
ie oad — sero

S
a -
: j
iP. ‘We @
siGme,
on (e0
Ae”
a ¢ Com pe, : >

: —— > i=? Zi, a 2.=7) OF

i ~— ae aT tas
—.
Ce eS GSS bem ono Ses

™ Pati’
Ex, "Ol Ses
Author Index

(Authors cited in the bibliographies at the ends of the chapters.)

Abragam, A., 153 Estabrooks, P. G., 178

Arfken, G., 36 Eyring, H., 12
Atkins, P. W., 12, 47, 153
Feynman, R. P., 36, 47, 62, 84, 272
Barker, W. A., 178 Foldy,, LoL. .110,1536,154,.272
Bethe HA... 173, 180: 19222247
292. Glover, F. N., 178
Bloch, C., 192 Goldstein, H., 47, 62, 103
Breit, G., 224 Goudsmit, S. A., 12
Brown, J. M., 193 Grandy, W. T., Jr., 239, 240, 264,
272
Carrington, A., 178, 193 Grant, I. P., 224
Case, K. M., 154
Chraplyvy, Z. V., 178 Hameka, H. F., 84, 103, 110, 239,
Corinaldesi, E., 224 264, 272
Coulson, C. A., 84, 269 Heitler, W., 264
Crane, H. R., 12 Howard, B. J., 192
Gross, Pace 192
Itoh, T., 178
Darwin, C. G., 84
Davies, D. W., 110 Jackson, J. D., 84
Decius. J.C. 192 Jamieson, A. M., 153
de Jeu, W. H., 224
Divager, A. Me. 125153, 224 Kettles Sm Ay al2
Kimball, G. E., 12
Eisberg, R. M., 84 Koskutov, Y. M., 178, 224
Eschbach,J. R., 193 Kusch, P., 12

2S
276 Advanced Molecular Quantum Mechanics

Landau, L. D., 12, 47, 62, 84, Sakurai, J. J., 103, 124, 153,
NOS), 272 224, 239, 240, 264, 272
Langenberg, D. N., 269 Salpeter, BE. Ex) 178s 1805192;
Leighton, R. B., 36, 47, 62, 84, 2245272
D2 Sands, M., 36, 47, 62, 84, 272
Levine, M. J., 178 Schiff, L. I., 240
Levy, Dal Us. 93 Series, G. W., 224
Lifschitz, E. M., 12,47, 62, 84, Shorey BD =aWalo2
LOS e202) Sikolov, A. A., 178, 224
Lowdin, P-O., 153, 154 Soliverez, C. E., 193
Strandberg, M. W. P., 193
Margenau, H., 36 Strocchi, F., 224
McGlaschan, M. L., 269 Sutcliffe, B. T., 178
McLachlan, A. D., 193 Szabo, A., 224
McWeeny, R., 12, 153, 178
Menzel, D. H., 192
Taylor, B. N., 269
Messiah, A., 192
edder i Me ain
Miller, T. Aq, 178, 193
Ternov, I. M., 178, 224
Moss, R. E., 154, 192
Thomas, L. H., 84
Murphy, G., 36
Murrell, J. N., 12, 224
Uhlenbeck, G. E., 12
Panofsky, W. K. H., 84, 103
Parker, W. H., 269
Van Vleck, J. H., 153, 193
Pauling, L., 12
Velenik, A., 224
Phillips, M., 84, 103
Powell, R. E., 224
Presenta ReaD tis Wallace, R., 264
Ine, Wil, lel, Ik. IOVS} Walter, J., 12
Wesley, J. C., 178
Ramsey, N. F., 192 Wilson, E. B., Jr:,.12, 192
Rich, A., 178 Wouthuysen, S. A., 153, 154
Rindler, W., 62, 84 Wright, J., 178
Rose, MoE. 12, 153, 154, 178;
224, 272
Royal Society (London) Symbols Ziman, J. M., 239
Committee 269 Zivkovic, T., 224
Subject Index

Little distinction is drawn between classical and quantum mechanics, since

classical theory is confined to Chapters 2 to 6 inclusive (pages 13 to 103).

absorption 243, 247, 250—252 many-electron atom 222

diagram 255 non-relativistic atomic orbitals
Einstein B coefficient 252 US AUNE
energy conservation 252 nodes 196, 216, 217
semiclassical theory 254 spherical harmonics 7, 196
transition rate 250—252 angular momentum 6—8, 45—46
see also two-photon processes additivity 46
action (integral) 39,57—58 commutation relations 6, 7
charge and field 64—6S, 90, constant of motion 45
92-93 eigenfunctions 7
continuous system 86—87 half-integral 7—8
electromagnetic field 90—92 operator 6
particle 58, 64 rotational 186—187
principle of least 38—39, 47, vibrational 186
$7—58 see also orbital and spin angular
additivity momenta
angular momentum 46 annihilation operator 233
electromagnetic fields 91 see also boson and fermion
momentum 45 operators, harmonic and radiation
Anderson 130 oscillators
angular functions anticommutation relations
associated Legendre polynomials Dirac operators 113—114
196 fermion operators 237—238
Dirac atomic orbitals 205, spin operators 9, 17
215-217 vector product 15, 18
nodeless 216—217 see also commutation relations

2a,
278 Advanced Molecular Quantum Mechanics

antimatter 131 operators 167—169

antiparticle 130 wave function components
see also positron 167
antisymmetric tensor, see Ejjp, Ea pys Foldy-Wouthuysen transfor-
associated Laguerre polynomials mation 166—174, 178
195 choice of 170—171
associated Legendre polynomials gauge invariance 166
196 lack of Lorentz invariance 165,
atom, see heavy atom, helium, 166
hydrogen, many-electron and matrix representation 165,
one-electron atoms 168—169
atomic method of small components
orbitals 166, 178
comparison 212—217, 224 non-relativistic approximation
Dirac 212—217, 224 166—174, 178
non-relativistic 195—196, 224 Breit operator 165—166, 178
radius 37 magnitude 166
spectroscopy 7, 8, 81, 172 quantum electrodynamics 165
axial vector 70 restriction on use 165, 166, 172,
188, 221
basis functions broadening of spectral lines 260—261
linear combination of 4
many-electron atom 221—223 calculus of variations 41
molecule 188, 223 canonical momentum 66
one-electron atom 198—200, density 87
201—204, 220—221 CGS units 63—64
black body radiation 225 charge 65
Bohr action 64—66, 90, 92—93
energy 11 conjugation operator y 129—130
magneton Ug 122, 269 conservation 25, 109—110
radius a, 132, 269 Dirac equation 127—128
Boltzmann law 254 Maxwell’s equations 94
Bose-Einstein statistics 11, density 25, 74, 92—93, 128
234-235, 237 dimensions 66, 267
boson 11, 234—235, 237 equation of motion 67
operators 237 generalization from particle 66
commutation relations 237 Hamiltonian 66, 106
photon 234—235 non-relativistic approximation
vibron 235 66.072
bound atomic states 207—211 Lagrangian 65—66
boundary conditions density 92—93
electromagnetic wave equation Lorentz equation 67
98—99 momentum 66
periodic 98—99 orbital angular momentum 72,
bra 2 106
Breit equation 155, 164—166, 178 see also moving and stationary
classification charges, two charges
Subject Index BUS
classical angular momentum 45 —46
field theory 85—103 continuous system 88—89
limit, radiation 235 energy 44, 89
mechanics 37—47, 48—49 momentum 44—45, 89
clock paradox 56 one-electron atom
closed system 43 Dirac theory 204—205
constants of motion 43—46 non-relativistic theory 195
commutation relations 5 contact interaction, see Fermi
angular momentum 6, 7 contact interaction
boson operators 233, 237 continuous mechanical system
conjugate variables 226—227 85—90, 103
Dirac Hamiltonian 123—124, action 86—87
204—206 canonical momentum density 87
electromagnetic field operators constants of motion 88—89
22) ALOE DSoRLSO equation of motion 86—88, 90
spin operators 8, 21 Lorentz invariance 88
see also anticommutation four-momentum 89, 90
relations Hamiltonian 89
commuting operators 5 density 87, 88, 90
components Lagrangian 86
Breit wave function 167 density 86, 90
Dirac atomic orbitals 212 momentum 89, 90
ratio large and small 208, 212 density 87—88, 90
large 134 contraction, Lorentz 54—55, 56
method of small 133—137, 142, contravariant component 62
143, 153, 166, 178 coordinates
negative energy 129, 134 generalized 37, 43, 44, 45, 86
positive energy 129, 134 molecular 185—186
small 134 normal 186
spinor 129 Coriolis coupling constants 186
configuration interaction 223 corrections, see radiative and
conjugate relativistic corrections
Hermitian 127 Coulomb interaction 160, 165, 177,
momentum 45, 66 182, 221—223
variables 226—227 lack of Lorentz invariance 165,
conservation of charge 25, 109—110 224
Dirac equation 127—128 Zitterbewegung correction 161,
Maxwell’s equations 94 Ay, tes?
conservation of energy 44 Coulomb gauge 71
time-dependent processes 246, Coulomb potential 212
D52-253,-256 coupled oscillators 86
conservation of number 109—110 covariant component 62
constants creation operator 232—234
fine structure 132, 269 see also boson and fermion
fundamental 268—269 operators, harmonic and radiation
Planck 3, 225, 269 oscillators
constants of motion 6, 43—46 cross product, see vector product
280 Advanced Molecular Quantum Mechanics

curl 23, 25—27 dipole-dipole interaction 163, 177

of r 29 nuclear hyperfine 182, 220
current 75 nuclear spin-spin 182
density 24, 74, 128 Dirac 104, 108, 111, 112, 130
dimensions 74, 267 Dirac bracket notation 2
displacement 75 Dirac atomic orbitals 212—217, 220,
four-vector 74, 92—93 222, 224
probability density 127 angular functions 205, 215—217
approximate analytic form
Darwin 79 213-215
Darwin term 143, 152—153, 177 comparison with non-relativistic
correction to Coulomb inter- 212—217, 224
action 161, 177, 182 degeneracies 200—201, 212, 217
one-electron atom 197, 200 heavy atom 212
Zitterbewegung 152—153 nodeless 213, 216—217
degeneracy normalization 209, 211
one-electron atom probability density 213—215,
Dirac theory 212, 217 216—217
non-relativistic approximation quantum numbers 205, 209—212
200—201 radial functions 205, 207—211,
non-relativistic theory 195 213
removal ratio of components 208, 212
Lamb shift 201, 212, 217—220 Dirac delta function 29—32, 36
many-electron atom 212, 223 dimensions 246
degenerate perturbation theory 192, expectation value 196
192—193 one-dimensional 30—31
Hermiticity 192, 193 representation 30—31, 246
degrees of freedom 37 three-dimensional 30, 32
del (V) 22—23 Dirac equation 111—154
delta function, see Dirac delta charge conservation 127—128
function charge density 128
6;; (Kronecker delta) 16—17 complete separation 131—132,
sum rule 17 133, 143-148
determinant 34—35 current density 128
Eijk 19, 34 derivation 112—114
vector product 14—15, 34 free electron 112—114, 123-125,
determinental wave function 221, 143—153, 154
222223 angular momentum 123-125,
diagrams 255, 264 150—152
absorption 255 position operator 145—146,
emission 255 149-150
two-photon processes 257—258 solution 143—144
scattering 258—259 velocity operator 144—145
diamagnetism 106,178 Zitterbewegung 145-146,
diffraction of X-rays 259 150, 151—153, 154
dilation of time 55, 56 gauge invariance 120
mu-mesons 56 introduction of fields 120
Subject Index 281
Lorentz invariance 125—128 Dirac operators 112—114
matrix representation 119 anticommutation relations
negative energy states 114, 119, 113-114
128—131, 142, 144, 148 charge conjugation 128—129
non-relativistic approximation matrix representation 114-119,
120—123, 131—143 168—169
expansion parameters 132 velocity 127, 144-145
Foldy-Wouthuysen transfor- Dirac representation 149—153
mation 131, 137—143, momentum 149
146-153 orbital angular momentum 151
gauge invariance 133 position 149—150
interpretation of terms 143 spin angular momentum 151
method of small components Dirac theory 130—131
131,133—137,142, 143, 153 interaction of radiation and
one-electron atom 197—201 matter 241, 243
truncation 133 many-electron atom 221—223
one-electron atom 194, 204—217, Maxwell’s equations 131
224 molecules 223—224
positive energy states 119, nuclear hyperfine interaction
129—130, 142, 148 220—221
positron 114, 128—131 nuclei 179—180
probability density 127 quantum electrodynamics 131
probability current density 127 vacuum state 131
relation to Klein-Gordon displacement current 75
equation 113—114,119 divergence 23, 24—25
similarity transformation 118—119 of r 29
spin 120—124 of r/r? 29, 32
angular momentum 123—124 Doppler effect 261
g factor 124, 174 dot product, see scalar product
magnetic moment 120—122
spinor 119, 129
wave function 119 effective Hamiltonian 188—192, 193
Dirac Hamiltonian 120 basis functions 188
commutation relations 123—124, degenerate perturbation theory
143—144, 151, 204—205 L293
one-electron atom 204 molecular parameters 189, 192
constants of motion 204—205 g factor 191
magnitude of terms 132—133, rotational constant 190—191
180 eigenfunction 2
polar coordinates 206—207 harmonic oscillator 232
Dirac matrices 114—119 Hermitian operator 3
charge conjugation 128—129 matrix 36
dimensionality 115—116 one-electron atom
equivalent representation 117 Dirac theory 205
Hermiticity 118 non-relativistic approximation
standard representation 118, 119 201—204
trace 115 non-relativistic theory 195—196
282 Advanced Molecular Quantum Mechanics

radiation oscillator 232 interaction with

eigenvalue 2 charge 63—84
harmonic oscillator 232 moving magnetic moment 72,
matrix 36 81—84, 143,177
one-electron atom introduction in Dirac equation
Dirac theory 211—212 120
non-relativistic approximation Lagrangian density 90—92
200—201 Lorentz transformation 68—70
non-relativistic theory 195 magnitude in atom 132—133
radiation oscillator 232 momentum 94—95, 101, 102
eigenvector, see eigenfunction moving electron 162—163
Einstein 54, 225 orthogonal to wave vector 100
principle of relativity 48—49 Poynting vector 95
Einstein coefficients quantization 225—230, 239
A 253 relation to potentials 67
absorption 252, 254 stationary charge 75—76
18} DSW, DNS} uniform 71—72
Planck’s radiation law 254 see also quantum theory of
spontaneous emission 253, 254 radiation, radiation oscillator
stimulated emission 253, 254 electromagnetic potentials 64—66
electric dimensions 66, 267
charge, see charge four-vector 65, 90
dipole moment, molecular 248 gauge transformation 70—71
dipole transition 248 Liénard-Wiechert 77
displacement D 68 Lorentz transformation 65
field gradient tensor 184 magnetic moment 157—158
field strength E 67—68 moving charge 76—79
see also electromagnetic fields moving electron 156—159
potential 65 relation to fields 67
see also electromagnetic retarded 77
potentials stationary charge 76
quadrupole moment uniform fields 71—72
molecular 249 electromagnetic wave equation
nuclear 183—185 95—99, 101—102
quadrupole transition 249 boundary condition 98—99
electrodynamics, see quantum damping terms 96
electrodynamics free space 96—99, 101—102, 109
electromagnetic fields 67—76, 85—103 gauge transformation 96—97
action 90—92 Klein-Gordon equation 109
additivity 91 separation of variables 97—98
characteristic vibrations 100—102 electromagnetic waves 95—102
conjugate variables 102, 226—227 fields 100
dimensions 68, 267 polarization vectors 98
equations of motion 90—92, 93 potentials 98—99
four-tensor 68—69 orthonormalization 98—99,
invariants from 70, 91 100
Hamiltonian 94—95, 100—101, 102 wave vector 97—99
Subject Index 283

see also radiation oscillator Thomas precession 81—84

electron Zeeman interaction 122, 143, 153 rd

fermion 237—239 LT,

mnetml Le TsOno 21 electron-electron interaction
interaction with radiation Coulomb repulsion 160, 165, 177,
241—243, 247-250 221—223
moving Darwin-type term 161, 177
fields 162—163 retarded orbit-orbit 162, 164,
potentials 156—159 oer
radius 37 spin-orbit 11, 84, 143, 161, 164,
rest energy 143, 177 177A 197 200
rest mass 269 spin-other-orbit 162, 163, 164,
reduced mass in atom 194, 220 heree
total angular momentum spin-spin 163, 177
124-125, 151 see also Breit equation, two
unsatisfactory wave equations electrons and many electrons
104—106, 111—112 electronic
see also Dirac equation, free contribution to rotational
electron, two electrons and many constant 191
electrons motion in molecule 185—186
electron orbital motion wave function test 189, 192
angular momentum 7, 72, 106, electron-nuclear interaction
150-151 181—183, 187
g factor 7 Coulomb attraction 182
magnetic moment 7, 72, 106 Darwin-type term 182
Zeeman interaction 106, 178 quadrupole 182
electron spin 8—11, 12, 120—125 retarded orbit—orbit 182
angular momentum 8, 11, spin-orbit 182
123—125, 150-151 spin-other-orbit 182, 187
Zitterbewegung 151—152 spin-rotation 187
contribution to fields 162 spin-spin 182, 220—221, 224
contribution to potentials spin-vibration 182
157—158 electron-positron pair 130—131,
Dirac theory 120—125 175-176
function 8,9, 188, 197 emission 243, 247, 252—253
g factor 10,11, 12, 124, 174-176, diagram 255
178, 269 Einstein A and B coefficients
magnetic moment 8, 11, 120—122 253
interaction with electric field energy conservation 253
143,177 semiclassical theory 254
matrices 9 spontaneous 253
models 10, 151—152 stimulated (induced) 253
operators 8—9 transition rate 253
anticommutation relations 9, see also two-photon processes
17,114 CAnalieOs
commutation relations 8, 21 energy
matrix representation 9, 114 conservation 246
284 Advanced Molecular Quantum Mechanics

constant of motion 44 expectation values 2, 3

four-momentum time com- one-electron atom 196—197
ponent 60-61 time dependence 5—6
Hamiltonian 46 vacuum state 236
kinetic 43, 44, 106, 143, 177,
182 Fermat’s principle of least time 39,
relativistic correction 106, 47
Ae) I, Wal, ACO Fermi contact interaction
mass as 59 electron-electron 163, 177
negative 108, 111, 128 nuclear hyperfine 182, 220—221,
operator 3 224
origin shift 105, 133 restriction on use 220, 224
photon 234 Fermi-Dirac statistics 11, 237-238
potential 43, 44 fermion 11, 237—239
rest 59, 143, 177, 182 exclusion principle 237 —238
total 44, 45 operators 237—239
zero-point 219, 233, 235—236 anticommutation relations
energy levels, see eigenvalues 237-238
€ijk 17—20 second quantization 237—239
determinental definition 19, 34 vacuum state 238
sum rules 19—20, 271 fields
vector product 17—18, 34 scalar 22, 89
Eg pys 62,91 self-consistent 221, 223
equations of motion 38 vector 22, 90
charge 67 see also electromagnetic fields
continuous system 86—88, 90 fine structure constant a 132, 269
electromagnetic field 90, 91, Fitzgerald contraction 55
92793 fluctuations, see vacuum fluctuations
Hamilton’s 46 fluorescence, resonance 260—264
Heisenberg’s 6 Foldy-Wouthuysen representation
Lagrange’s 39—41 149-153
Lorentz 67 Darwin term 152—153
particle 43 momentum 149
GQ, Os! orbital angular momentum 151
Euler’s equations 41 position 149-150, 151, 152
even operator 138 spin angular momentum 151
even-even operator 167—169 Zitterbewegung 150, 151—153
even-odd operator 167—169 Foldy-Wouthuysen transformation
exchange interaction 223 Breit equation 166—174, 178
excited state lifetime 5, 261—263 choice of transformation
imaginary part 263 170-171
Lamb shift 263 classification of operators
natural line width 261 167-169
real part 263 transformed Hamiltonian 172,
uncertainty principle 261 173-174
exclusion principle 11, 12, 237—238, Dirac equation 131, 137—143,
239 13
Subject Index 285

even operator 138 velocity operator 127, 144-145,

odd operator 138 150
transformed Hamiltonian 141, Zitterbewegung 145—146,
142—143 149-150, 151-153, 154
free electron 142, 146—153, 154 amplitude 146, 153
mean operators 150—152, 154 frequency 145—146
transformed Hamiltonian 148 free space, see vacuum
Zitterbewegung 150, 151—153, freedom, degrees of 37
154 frequency
Hamiltonian 139, 146, 169 Larmor 81
operator 149 Thomas 83
wave function 139, 169 Zitterbewegung 145—146
force 43 fundamental constants 268—269
four-current 92—93
four-dimensional space 36, 49, 51—53,
60 g factor (g value) 7
four-momentum 60—61 electron spin 10, 11, 12, 124, 178
continuous system 89 Dirac theory 124, 174
field 95, 101, 102 experimental value 174, 178,
four-position 60 269
four-potential 65, 90 models 10, 151—152
four-tensor 61—62 radiative corrections 174—176,
electromagnetic field 68—69 178, 239
antisymmetry 69 theoretical value 175, 176,178
invariants from 70, 91 molecular
Lorentz transformation 62 effective Hamiltonian 191
unit antisymmetric, see €yg75 spin-orbit interaction 191
four-vector 36, 60—62 neutron 181
Lorentz transformation 60 nuclear 181
scalar product 60 orbital 7
four-vector operator 0/drg 61 proton 181
frame of reference 37—38 Galileo’s relativity principle 38
inertial 38 Galilean transformation 38, 48, 49
free electron invariance of physical laws 38
Dirac equation 112—114, 143-153, gamma function 211
154 gauge
Dirac position 149 Coulomb (radiation) 71, 97
Foldy-Wouthuysen transformation Porentz 71,97
146-153, 154 gauge invariance 71
Hamiltonian 143—144, 148 Breit equation 166
mean orbital angular momentum Dirac equation 120
Syl quantum mechanical equations
mean position 145—146, 149—150, 107,110
152, 154 gauge transformation 70—71
mean spin angular momentum 151 electromagnetic potentials
mean velocity 145, 150 70—71, 78, 96—97
position operator 145—146, 149 Lagrangian 71
286 Advanced Molecular Quantum Mechanics

quantum mechanical equations molecular 179—193

107, 110 nuclear 181—182
wave function 107 particle 59
Gauss’ one-electron atom 197
law 32, 74, 94 two electrons 155, 159—164,
theorem 25 178
Gaussian (mixed CGS) system operator 3, 104
63—64, 66, 68, 75 radiation oscillator 102, 227—228
conversion to SI relation to Lagrangian 46
equations 267—268 spectroscopically useful 185—187,
units 268 192
general relativity 11 spin 191, 193
generalized two charges 80
coordinates 37, 86 Hamilton’s
force 43 equations of motion 46
momentum 45 principle 38
velocity 38 harmonic oscillator 230—232, 239
gradient 23—24 annihilation operator 233, 239
Of W729 creation operator 233, 239
gravitation 11 eigenfunctions 232
group, Lorentz 54 eigenvalues 232
gyroscopic motion 81 Hamiltonian 102, 228, 230
momentum 102
Hamiltonian 46—47, 59 momentum operator 232
Breit 166 number operator 232
charge 66 occupation number 232
continuous system 89 see also vibration
density 87, 90 heavy atom 11, 180, 212, 221
Dirac 120 Heisenberg
effective 188—192, 193 equation of motion 6
electromagnetic field 95, picture 5, 228
100—101, 102 relation to Schrodinger picture
Foldy-Wouthuysen transformation 5—6, 228
139, 146, 169 see also uncertainty principle
free electron 143—144, 148 helium 172
free particle 59 Hermitian
harmonic oscillator 102, 228, 230 conjugate 127
interaction of radiation and matter matrix 33
244, 264 operator 2—3
non-relativistic approximation Hermiticity 2—3
charge 72, 105—106 degenerate perturbation theory
Dirac 131—143 192, 193
electron-nuclear interaction Dirac matrices 118
181—183 method of small components
interaction of radiation and 136—137
matter 242—243, 264 two-electron Hamiltonian 156—157.
many electrons 176—178 162
Subject Index 287

hexadecapole moment 185 maximum velocity of propagation

Hilbert space 2 48—49
homogeneity of space and time 38 nuclear hyperfine 182, 220—221,
hydrogen atom 194—224 224
Dirac equation 194 nuclear quadrupole 182, 183—185
magnitude of terms 80, nuclear-nuclear 182
132—133 radiation and matter 225, 241—264
Lamb shift 217—220, 224 comparison of theories 254—255
nuclear hyperfine interaction Dirac theory 241, 243
220, 224 Hamiltonian 242—243, 264
see also one-electron atom matrix elements 247—250
hyperfine interaction, see nuclear semiclassical theory 225, 241,
hyperfine interaction 254
retarded orbit-orbit 162, 164,
idempotent operator 238 17, 182
induced emission, see stimulated spin-orbit 11, 84, 143, 161, 164,
emission LTT LED NE 97200
induction law 73 spin-other-orbit 162, 163, 164,
inertia tensor 187 GAIL, os, htst7/
inertial frame 38 spin-rotation 183, 187
inner electrons 11, 180, 212 spin-spin 163, 177, 182
intensity, radiation 251 spin-vibration 187
interaction three-body 176, 178
Breit 165—166 two charges 79—80, 84
charge and field 63—84, 106 Leeman 106122 4 sel oS eles 7,
action 64—66, 90, 92—93 7 Gels2
equation of motion 67 intermediate state 257
Hamiltonian 66, 72, 106 lifetime 257, 261, 264
Lagrangian 65—66 scattering 261, 264
Lagrangian density 92—93 two-photon processes
Lorentz equation 67 257-258
configuration 223 uncertainty principle 257, 261
Coulomb 160, 165, 177, 182, interval SO—51, 52
221—223 invariance
Darwin 143, 152—153, 161, 177, physical laws 38, 54
182, 197, 200 velocity of light 49, 51
diamagnetic 106, 178 see also Galilean, gauge and
dipole-dipole 163, 177, 182, 220 Lorentz invariance
electron and field 143, 177, isotope shifts 183
241—243, 247-250 isotropy of space 38
electron-electron 160—164, 177 Itoh 155, 176
electron-nuclear 181—183, 187
exchange 223 ket 2
Fermi contact 163, 177, 182, kinetic energy 43, 44
220—221, 224 charge 106
magnetic moment and field 72, electron 143, 177
81—84, 143, 177 nucleus 182
288 Advanced Molecular Quantum Mechanics

relativistic correction 106, 143, quantum electrodynamics

VT, WNT, ADO) 218—219, 263
Klein-Gordon equation 108—110 vacuum fluctuations 219
electromagnetic wave equation Laplacian (V7) 28
109 of 1/r 29, 32
Lorentz invariance 108 Larmor
mesons 109 frequency 81
negative energy solutions 108 precession 81
negative mass solutions 108 large components 134
relation to Dirac equation ratio to small components 208,
113-114, 119 212
time-dependent probability laser spectroscopy 256
density 108—109, 112 laws, see Boltzmann, Gauss’, induc-
unsuitability for electron 110, 112 tion, Newton’s and Planck’s laws
Kronecker delta, see 6;; Legendre polynomials 196
Liénard-Wiechert potentials 77
Lagrange’s equations of motion lifetime
39-41 excited state 5, 261—263
continuous system 86—88 intermediate state 257, 261, 264
Lagrangian 39 mu-mesons 56
addition of time derivative 41 light
charge and field 65—66, 92—93 Fermat’s principle 39
closed system of particles 42—43 velocity 49, 75, 269
continuous system 86 invariance 49, 50, 51
coupled oscillators 86 line
density broadening 260—261
charge and field 92—93 Lorentz shape 263—264
continuous system 86 natural width 261—264
electromagnetic field 90—92 linear
Lorentz invariance 91 combination of basis functions 4
free particle 41—42, 57-58 molecule 187, 192
Galilean invariance 42 operator 2
gauge transformation 71, 90 long wavelength approximation 247
invariance to displacement 44 Lorentz 54
invariance to rotation 45 contraction 54—55
Lorentz invariance 57—58 equation 67
molecular 187 gauge 71
non-relativistic approximation 58 group 54
relation to Hamiltonian 46 line shape 263—264
two charges 79—80, 160 Lorentz invariance
Laguerre polynomials 195 action 57—58, 65
Vambishitt 2015212) 217-2205 Dirac equation 125—128
224, 263 equation of motion for a con-
hydrogen atom 217—220 tinuous system 88
many-electron atom 220 four-tensor equations 62
model 219 four-vector equations 61
one-electron atom 201, 212, 220 four-vector scalar product 60
Subject Index 289

interval 50—51 heavy atom 180

Klein-Gordon equation 108 hydrogen 80, 132—133
Lagrangian 57—58 many electrons
Lagrangian density 91 Hamiltonian 176—178
Maxwell’s equations 54, 63, 73 quantum electrodynamics 176,
physical laws 54 178
Lorentz transformation 51—54 three-body interactions 176
electromagnetic fields 68—70 wave equation 155—178
energy 60—61 many-electron atom 221—224
four-tensor 62 angular functions 222
four-vector 60—61 configuration interaction 223
four-vector operator 0/drg 61 degeneracies 212, 223
general 54 determinental wave function
inverse 53 PLM PON DOS:
momentum 60—61, 125—126 Dirac theory 221—223
non-relativistic limit 53 exchange interaction 223
orthogonal transformation Lamb shift 220
$2—53, 61 non-relativistic theory 221
position 51—54 Pauli exclusion principle 222
probability density 127 radial equations 222
probability current density 127 self-consistent field 221, 223
time 51—54 variation principle 223
velocity 56—57 many-electron theory 239
mass
magnetic as energy 59
dipole moment negative 108
interaction with fields 72, 81, photon 234
143,177 polarization 187
nuclear 181, 185 reduced 194, 220
potentials 157-158 rest 59
see also orbital and spin mag- matrices, see Dirac and Pauli
netic moments matrices
dipole transition 249 matrix
flux density B 64, 67—68 adjoint (Hermitian conjugate) 33
see also electromagnetic fields algebra 33—36
field strength H 64, 68 cofactor 35
monopole 73, 185 complex conjugate 33
potential 65 determinant 34
see also electromagnetic diagonal 33
potentials diagonalization 36
resonance 182, 188, 249 eigenvalues 36
magneton eigenvectors 36
Bohr 122, 269 Hermitian 33
nuclear 181, 269 Hermitian conjugate (adjoint) 127
magnitude inverse 34, 35
Breit operator 166 multiplication 33
terms in Dirac equation orthogonal 34
290 Advanced Molecular Quantum Mechanics

product second pair 74—75, 93-94

Hermitian conjugate 127 mean
inverse 34 orbital angular momentum 151
trace 34 position 145—146, 149—150, 151,
transpose 33 152, 154
representation spin angular momentum 151
Breit equation 165, 168—169 velocity 150
Dirac equation 119 mechanical momentum 66
Dirac operators 114-119, mechanics
168—169 classical 37—47, 48—49
equivalent 117 relativistic 57—59
spin operators 9, 114 meson 56, 109
spinors 119, 167 theory 181
similarity transformation 36, 115 method of small components
singular 35 Breit equation 166, 178
trace 34 Dirac equation 131, 133—137, 142,
transpose 33 143, 153
unit 33 transformed Hamiltonian 137,
unitary 34 142
matrix element 2 Hermiticity 136—137
electric dipole moment 248 renormalization of wave function
electric quadrupole moment 136—137
248—249 Michelson-Morley experiment 49
interaction Hamiltonian 247—250 microwave spectroscopy 188, 256
long wavelength approximation mixed system of units, see Gaussian
247 system
magnetic dipole moment 249 MKSA units 64, 265
momentum 247—248 see also SI
polarizability tensor 260 molecular
reaction 245—246, 255 beam spectroscopy 183
spin operators 9 coordinates 185—187, 192
matter electric dipole moment 248
wave-particle duality 235, 239 electric quadrupole moment 249
see also interaction with radiation Hamiltonian 179—193
maximum velocity of interaction effective 188—192, 193
propagation 48—49 spectroscopically useful
Maxwell’s equations 72—75, 93—94 185—187, 192
charge conservation 94 Lagrangian 187
Dirac theory 131 orbitals 223
electromagnetic waves 95—97 parameters 189, 192
first pair 72—74, 75 g factor 191
four-tensor notation 73, 74 rotational constant 189—191
Gauss’ law 32, 74, 94 polarizability 259—260
induction law 73 rotation 185, 186
Lorentz invariance 54, 63, 73, 74 Schrodinger equation 188—189
quantum theory of radiation spin-rotation interaction 183, 187
229—230 spin-vibration interaction 187
Subject Index 2911

translation 185, 186 multiplication, see matrix and vector

vibration 185, 186 multiplication
molecule mu-meson 56
electronic theory 223—224
interaction with radiation 248,
249, 250-261 natural line width 261—264
linear 187, 192 lifetime excited states 261—263
spherical 190—191 uncertainty principle 261
momentum 45, 59 negative energy
additivity 45 components 129, 134
canonical 66 states 108, 111, 128
charge 66 Dirac equation 114, 119,
conjugate 45, 66 128—131, 142, 144, 148
constant of motion 44—45 see also positron
continuous system 89, 90 negative mass 108
density, continuous system 87—88, see also negative energy states
90 neutron 181
electromagnetic field 94—95, 101, Newton’s laws 38, 41, 49, 57
102 first 42
four-vector 60—61 second 43, 57
generalized 45 third 45
harmonic oscillator 102 nodes, one-electron atom
matrix element 247—248 angular functions 196, 216
mechanical 66 probability density 196,
operator 3, 104 213—215, 216-217
harmonic oscillator 232 radial functions 195, 213
radiation oscillator 229 uncertainty principle 196
photon 234 non-relativistic approximation
radiation oscillator 102 Breit equation 166—174, 178
translational 186 Dirac equation 120—123,
vibrational 186 131-143, 153
see also angular momentum moving charge potentials 78
monopole, magnetic 73, 185 one-electron atom 197—201
Mossbauer spectroscopy 183 relativistic equations 105—106
motion, see constants and equations two-charge interaction 79—80
of motion two-electron Hamiltonian
moving charge potentials 76—79 159-164
moving electron non-relativistic atomic orbitals
fields 162—163 212—217, 224
potentials 156—159 angular functions 195, 196, 216
moving magnetic moment comparison with Dirac 212—217,
interaction with field 72, 81—84, 224
VASE lies. degeneracies 195
potentials 157—158 nodes 196, 213, 216, 217
multiphoton processes 256—260 probability density 196, 213, 215
see also scattering, two-photon quantum numbers 195
processes radial functions 195, 213
292 Advanced Molecular Quantum Mechanics

non-relativistic quantum mechanics large atomic number 180, 221

1-12 nuclear-electron interaction, see
many-electron atom 221 electron-nuclear interaction
molecular orbitals 223 nuclear-nuclear interaction 182—183
one-electron atom 194—197 Coulomb repulsion 182
unsatisfactory features 11—12 spin-rotation 183
normal coordinates 186 spin-spin 182
normalization 2 number
Dirac orbitals 209, 211 conservation 109—110, 239
electromagnetic waves 98—99, density, wave vector 99
100 operator 232
method of small components commutation relations 233,
136—137 236
nuclear fermion 238
electric moments 185 harmonic oscillator 232
quadrupole 183—185 radiation oscillator 233
g factor 181
Hamiltonian 181—182
hyperfine interaction observable 2
dipole-dipole 182, 220 occupation number 232
Fermi contact 182, 220, 224 octupole moment 185
relativistic correction 221, 224 odd operator 138
kinetic energy 182 odd-even operator 167—169
magnetic moments 185 odd-odd operator 167—169
dipole 181, 185 one-electron atom
magnetic resonance 182 Lamb shift 201, 212, 220, 224
magneton 181, 269 nuclear hyperfine interaction
quadrupole 220—221, 224
interaction 181, 182, 183—185 relativistic correction 221
tensor 184 see also hydrogen atom
radius 37 one-electron atom, Dirac theory
rest energy 182 197—221, 224
size effects 183-185, 192 angular functions 205, 215—217
isotope shifts 183 bound states 207—211
Mossbauer spectroscopy 183 constants of motion 204—205
quadrupole interaction degeneracies 212, 217
183-185 eigenvalues 211—212
spin 10, 179, 180—181, 183, 220 Hamiltonian 204
angular momentum 180 commutation relations
function 188 204—205
g factor 181 non-relativistic approximation
magnetic moment 181 197—205
Zeeman interaction 182 angular functions 201—204
states, parity 184, 185 Darwin-type term 197, 200
nuclei 179—185 degeneracies 200—201
as Dirac particles 179—180, 192 eigenvalues 200—201
restrictions 180, 192 Hamiltonian 197
Subject Index 293

quantum numbers 198—199, odd 138, 167—168

201—202 position 3
radial functions 202 spin 8
relativistic correction to kinetic vector (V) 22—23
energy 197, 200 optical rotation 259
spin-orbit interaction 197, 200 orbital
total angular momentum 198 angular momentum 7, 72, 106,
normalization 209, 211 123-125, 151
nuclear hyperfine interaction atomic 195—196, 212—217, 224
220—221 g factor 7
polar coordinates 206—207 magnetic moment 7, 72, 106
quantum numbers 205, 209—212 molecular 223
radial functions 205, 207—211, Zeeman interaction 106, 178
203 orbit-orbit interaction, retarded 162,
radial equations 207—211 164, 177, 182
total angular momentum 204 orthogonal
see also Dirac atomic orbitals { matrix 34
one-electron atom, non-relativistic transformation 52—53, 61
theory 194—197 orthogonality 2
angular functions 195, 196, 216 electromagnetic waves 98—99,
constants of motion 195 100
degeneracies 195 Hermitian operator eigenfunctions
eigenvalues 195 3
expectation values 196—197 wave vector
nuclear hyperfine interaction and fields 100
220 and polarization vectors 98
quantum numbers 195 vectors 14
radial functions 195, 213 oscillators
see also non-relativistic atomic coupled 86
orbitals see also harmonic and radiation
operator 2, 3 oscillators
angular momentum 6 oscillatory motion, see
annihilation 233, 239 Zitterbewegung
charge conjugation 129—130 overlap integral 4
creation 233, 239
electromagnetic field 228 paradox, clock 56
energy 3 parity of nuclear states 184, 185
even 138, 167—168 particle
field momentum 229 free
four-vector 0/drg 61 equations of motion 43
Hamiltonian 3 Hamiltonian 59
Hermitian 2—3 Lagrangian 41—42, 57-58
idempotent 238 quantization 3, 104, 226
linear 2 see also charge
mean 149-151 Pauli exclusion principle 11, 12,
momentum 3 237-238, 239
number 232, 233, 238 Pauli spin matrices 9, 114, 116
294 Advanced Molecular Quantum Mechanics

permeability of a vacuum Up 64, 75, Foldy-Wouthuysen representation

269 149=1S5O"US ia ls2
permittivity of a vacuum €9 64, 74, Galilean transformation 38
269 Lorentz transformation 51—54
relation to Ug 75 mean 145—146, 149-150, 151,
permutation symbol, see €;jp, €a py 152, 154
perturbation theory 4—5 operator 3
see also degenerate and time- vector 29, 37
dependent perturbation theories positive energy
phase factor of wave function components 129, 134
energy origin shift 105, 133 state 119, 129—130, 142, 148
gauge transformation 107 positron 128—131
photoelectric effect 225 magnetic moment 175
photoelectron spectroscopy 11, 221 potential
photon 234—235 Coulombic 212
absorption 250—252, 254-255, four-vector 65, 90
256-257 non-Coulombic 212, 222, 223
Bose-Einstein statistics 234—235 scalar 65
classical limit 235 vector 65
emission 252—253, 254-255, see also electromagnetic potentials
256 potential energy 43, 44
energy 234 Poynting vector 95
mass 234 precession
momentum 234 Larmor 81
scattering 258—260 Thomas 81—84, 143
spin 235, 239—240 pressure broadening 261
vacuum state 234, 235—237 principle
VirtualaliGs= lia 203 exclusion 11, 12, 237—238, 239
see also quantum theory of Fermat’s 39, 47
radiation Hamilton’s 38
Planck 225 Heisenberg’s 5
constant 3, 225, 269 least action 38—39, 47, 57—58
radiation law 254—255 least time 39, 47
polar vector 70 Pauli 11, 12, 237—238, 239
polarizability, molecular 259—260 relativity
tensor 260 Einstein’s 48—49, 54
polarization Galileo’s 38, 54
mass 187 uncertainty 5
vector 98 variation 4
orthogonal to wave vector 98 probability
sum over 251—252 amplitude 2
polynomials current density 127
associated Laguerre 195 density 1
associated Legendre 196 atomic orbitals 196, 213—215,
position 216—217
Dirac representation 149—150 Dirac atomic orbitals 213—215 )}
four-vector 60 216-217
Subject Index aS

Dirac equation 127 field momentum operator 229

Klein-Gordon equation Hamiltonian 227, 229
108—109, 112 Heisenberg picture 228
Lorentz transformation 127 interaction of radiation and
time-dependent 108—109, 112 matter 241—264
product, see matrix, scalar and comparison of theories
vector products 254-255
proton 181 Hamiltonian 242—243, 264
charge 269 see also absorption, emission,
rest mass 269 scattering, two-photon processes
pseudoscalar 70 Maxwell’s equations 229—230
photons 234—235
quadrupole, see electric quadrupole Planck radiation law 254—255
quantization Schrodinger equation 227
electromagnetic field 225 —230, Schrodinger picture 228
239 vacuum fluctuations 235—237,
particle 3, 104, 226 240, 254
second 237—239, 240 Lamb shift 219, 237
quantum electrodynamics vacuum state 233—234, 235—237
Breit interaction 165 zero-point energy 219, 233,
Dirac theory 131 235-237
electron g factor 174—176, 178, see also radiation oscillator
239
Lamb shift 218—219, 224, 263 radial equations
many electrons 176, 178 many-electron atom 222
nuclei 180, 192 one-electron atom
second quantization 237—239, Dirac theory 207—211
240 non-relativistic theory 207
two electrons 155, 174 radial functions
quantum field theory, see quantum Dirac atomic orbitals 205,
electrodynamics, quantum theory 207-211, 213
of radiation nodeless 213
quantum mechanics, non-relativistic normalization 209, 211-
1-12 non-relativistic atomic orbitals
quantum numbers, one-electron atom 195
Dirac theory 205, 209-212 nodes 195, 213
non-relativistic approximation radiation
198—199, 201—202 black body 225
non-relativistic theory 195 classical limit 235
quantum theory of radiation Einstein 225
225—264 gauge 71
classical limit 235 intensity 251
conjugate variables 226—227 interaction with matter 225,
commutation relations 227 241
electromagnetic field operators comparison of theories
228 254-255
commutation relations 236 quantum theory 241—264
296 Advanced Molecular Quantum Mechanics

semiclassical theory 254 spin Zeeman interaction 143,

photoelectric effect 225 Way), PAT
Planck 225 Hamiltonian, free particle 59
Planck’s law 254—255 invariance, see Lorentz invariance
ultraviolet catastrophe 225 Lagrangian, free particle 57—58
wave-particle duality 235, 239 mechanics 49, 57—S9
see also quantum theory of momentum, free particle 59
radiation, radiation oscillator theory, need for 11—12
radiation oscillator 102, 227—228 wave equations 104—110
annihilation operator 233 relativity
creation operator 233 general 11
eigenfunctions 233 principle
eigenvalues 233 Einstein’s 48—49, 54
Hamiltonian 102, 227, 229 Galileo’s 38
momentum 102, 229 special 11, 48—62
number operator 233 renormalization, method of small
occupation number 233 components 136—137
Schrodinger equation 227 repeated subscript summation con-
zero-point energy 233, 235—237 vention 15—16
radiative corrections 155 representation
electron g factor 174-176 Dirac 149-153
Lamb shift 217—220 Dirac delta function 30—31, 246
radio-frequency spectroscopy 256 Foldy-Wouthuysen 149—153
radius, Bohr 132, 269 separable 188
Raman scattering 258—259 standard 118,119
rationalized units 64 see also matrix representation
see also SI resonance
Rayleigh scattering 250, 258—260 fluorescence 260—264
molecular polarizability 259—260 magnetic 182, 188, 249
reaction matrix element 245-246 rest energy 59
diagrams 255 electron 143, 177
scattering 259 nuclear 182
two-photon absorption 256 rest mass 59
reduced mass of atomic electron retarded
194, 220 orbit-orbit interaction 162, 164,
reference frame 37—38 NIE, {tes22
relativistic potentials 77
corrections rotational
heavy atom 11, 180, 212, 221 angular momentum 186—187
kinetic energy 106, 143, 177, constant 190—191
197 -200R221 wave function 188, 189
nuclear hyperfine interaction
221, 224 scalar
one-electron atom 11, 180, field 22, 89
197—201, 220 potential 65
orbital Zeeman interaction see also electromagnetic
106 potentials
Subject Index 297
product space
four-vectors 60 four-dimensional 36, 49, 51—53
vectors 14, 15—16 homogeneity 38
scattering 243, 258—260 isotropy 38
diagrams 258—259 special relativity 11, 48—62
intermediate states 261, 264 Einstein’s principle 48—49
Raman 258—259 see also Lorentz transformation
Rayleigh 250, 258—260 spectral line
reaction matrix element 259 broadening 260—261
resonance fluorescence 260—264 Lorentz shape 263—264
X-ray diffraction 259 spectroscopically useful Hamiltonians
Schrodinger 146 185—187, 192
Schrodinger equation 3—5 spectroscopy
time-dependent 3, 109 atomic 7,8, 81,172
time-independent 4—5 isotope shifts 183
Schrodinger picture 5, 228 laser 256
relation to Heisenberg picture magnetic resonance 182, 188,
S5—6, 228 249
time-dependent perturbation microwave 188, 256
theory 244 molecular beam 183
second quantization 237—239, 240 Mossbauer 183
self-consistent field 221, 223 radio-frequency 256
semiclassical theory 225, 241, 254 X-ray photoelectron 11, 221
comparison with quantum theory spherical harmonics 7, 196
254-255 spin 8
Planck radiation law 254—255 Hamiltonian 191, 193
separable representation 188 photon 235, 239—240
SI 64, 66, 68, 74, 75, 91, 265—269 see also electron and nuclear spin
advantages 64 spinor 119
base units 265 components 129
conversion from Gaussian system spin-orbit interaction 11, 161, 164,
267—268 177A S21972200
decimal multiples 267 molecularg factor 191
derived units 266 Thomas factor 84, 143
dimensions 265—267 spin-other-orbit interaction 162,
fundamental constants 268—269 163, 164, 177, 182, 187
rationalized units 64 spin-rotation interaction 187
supplementary units 266 spin-spin interaction 163, 177, 182
similarity transformation 36 see also Fermi contact interaction
anticommutation relations 115 spin-vibration interaction 187
Dirac equation 118 spontaneous emission 253, 254
trace 115 Einstein A coefficient 253
size effects, nuclei, see nuclear size state
effects bound 207—211
small components 134 stationary 4
ratio to large 208, 212 see also intermediate, negative
see also method of small com- energy, positive energy and
ponents vacuum states
298 Advanced Molecular Quantum Mechanics

stationary charge transition rate 246

fields 75—76 two-state system 262—264
potentials 76 total angular momentum of electron
stationary state 4 124-125, 151
statistics trace of a matrix 34
Bose-Einstein 11, 234—235, 237 invariance to similarity transfor-
Fermi-Dirac 11, 237—238 mations 115
stimulated emission 253, 254 transformation
Einstein B coefficient 253 Galilean 38, 48, 49
Stokes’ theorem 27 orthogonal 52—53, 61
sum rules similarity 36,115,118
unitary 139, 146, 169
€ijk 19—20, 27 see also Foldy-Wouthuysen, gauge
summation convention 15—16 and Lorentz transformations
surface element 25 transition
Systeme International d’Unités, see electric dipole 248
SI electric quadrupole 249
magnetic dipole 249
tensor natural line width 261—264
electric field gradient 184 rate 246
electric quadrupole absorption 250—252
molecular 249 emission 253
nuclear 184 translational
inertia 187 momentum 186
molecular polarizability 260 wave function 188
unit antisymmetric, see €jjp, Eagys triple product of vectors 18—19,
see also four-tensor 20—21, 270
Thomas two charges 79—80, 84
factor 84, 143 in external fields 80
frequency 83 Hamiltonian 80
precession 81—84, 143 Lagrangian 79—80, 160
three-body interactions 176, 178 two electrons
time Hamiltonian 155, 159-164,
absolute 38, 48 173-174, 178
dilation 55,56 Hermiticity 156—157, 162
mu-mesons 56 see also Breit equation
fourth dimension 36, 49, 51, 60 two-photon processes
homogeneity 38 absorption 243, 256—258
principle of least 39, 47 diagrams 257—258, 264
relative 49 energy conservation 256
time-dependent perturbation theory emission 243, 256, 257—258
243-247, 264 intermediate states 257
deficiencies 246—247, 260—261 reaction matrix element 256
energy conservation 246 see also scattering
initial conditions 244, 245, 262 two-state system 262—263
reaction matrix element 245—246 energy shift 263
Schrodinger picture 244 excited state lifetime 263
Subject Index 299
line shape 263—264 algebra 13—32, 36
axial 70
ultraviolet catastrophe 225 component 13—14
uncertainty principle 5 contravariant and covariant 62
energy and time 5 differentiation 22—32, 270-271
intermediate states 257 curl 23, 25—27
momentum and position 5 divergence 23, 24—25
natural line width 261 gradient 23—24
nodes in atomic orbitals 196 Laplacian (V7) 28
zero-point energy 236 of products 27—28, 270
unit field 22, 90
antisymmetric tensor, see €ijk> Hilbert space 2
fapyd integral relations
orthogonal vectors 13—14, 15 Gauss’ theorem 25
unitary Stokes’ theorem 27
matrix 34 length 14
transformation 139, 146, 169 multiplication 14—22
units 63—64, 265—269 operator
CGS 63—64 del (V) 22—23
conversion 268 Laplacian (V7) 28
e.m.u. and e.s.u. 63 orthogonal 14
Gaussian (mixed CGS) 63—64, polar 70
268 position 29, 37
MKSA 64 potential 65
rationalized 64 see also electromagnetic
SI 64, 265—269 potentials
see also SI Poynting 95
product 14
vacuum anticommutivity 15, 18
permeability Up 64, 75, 269 determinental definition
permittivity €9 64, 74, 75, 269 14-15, 34
vacuum fluctuations 235—237, 240 €ijk 17-18, 34
Lamb shift 219, 237 second derivatives 28, 270
spontaneous emission 254 triple products 18—19, 20—21,
vacuum state 270
Dirac theory 131 unit orthogonal 13—14
fermion 238 scalar product of 14, 16
fluctuations 235—237, 240 vector product of 15, 18
radiation 233—234, 235-237 useful relations 270—271
expectation values 236 see also four-, polarization and
field momentum 235 wave vectors
Lamb shift 219, 237 velocity
spontaneous emission 254 generalized 38
uncertainty principle 236 light 49, 75, 269
zero-point energy 235—237 invariance 49, 50, 51
variation principle 4 Lorentz transformation 56—57
vector 13—14 maximum 48—49
300 Advanced Molecular Quantum Mechanics

operator gauge transformation 107

free electron 144-145 spinor 119
mean 150 wave vector 97
vibration number density 99, 251
characteristic of field 100—102 orthogonal to
uncertainty principle 236 fields 100
zero-point energy 236 polarization vectors 98
see also harmonic oscillator sum over as integral 99, 251
vibrational wave-particle duality 235, 239
angular momentum 186 world
coordinate 186 line 49, 55
momentum 186 point 49, 60
wave function 188
vibron 235 X-ray diffraction 259
vibronic state 188. X-ray photoelectron spectroscopy
virtual 1, 2ai|
electron-positron pair 175—176
meson field 181 Zeeman interaction
photon 165, 175, 263 electron
state, see intermediate state orbital 106, 178
spin 122, 143, 153, 177
wave equation nuclear 182
gauge invariance 107 relativistic correction 106, 143,
gauge transformation 107 LPSSmivii
linear in 0/dt 109 zero-point energy
many electrons 155—178 radiation 219, 233, 235—237
quadratic in 0/dt 109 uncertainty principle 236
relativistic 104—110 vibration 236
see also Breit, Dirac, electromag- Zitterbewegung 145 —146, 150,
netic wave, Klein-Gordon and 151-153, 154
Schrodinger equations amplitude 146, 153
wave function 1—2 Coulomb interaction correction
acceptable 2 161
determinental 221, 222, 223 Darwin term 152—153
electronic, test of 189, 192 electron spin 151—152
normalization 2 Foldy-Wouthuysen representation
orthogonality 2 150, 151—153
phase factor frequency 145—146
energy origin shift 105, 133 model 151—152
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Studies in Chemical Physics
A series edited by A. D. Buckingham, Professor of.
Theoretical Chemistry, University of Cambridge

Electronic Transitions and the High Pressure

Chemistry and Physics of Solids
H. G. Drickamer and C. W. Frank
The most general effect of pressure is to increase overlap of
electronic orbitals. An important consequence of this increased
overlap is the shift in energy of one type of orbital with respect to
ancther. In a very wide variety of cases this shift is sufficient to
provide a new ground state for the system which may have very
different physical and chemica! properties. Although this book
discusses the physica! consequences of these electronic transitions,
it iays greater emphasis on the chemical effects and in so doing
seeks to provide a common thread in a wide variety of apparently
disparate observations.
The first part of the book contains an account of the theoretical
background necessary for understanding the observations, while
the second part of the book is concerned with the observations
themselves. This work will be invaluableto many workers in
chemical physics and solid state physics. It will interest experiment-
alists in new topics which are barely scratched or completely
untouched. Theoreticians will find here a most broad and fertile
field for further analysis.
CONTENTS: Introduction; Theories of Electronic Energy Levels in
Molecules and Solids; Thermal vs Optical Transitions; Phenomeno-
logical Description of Continuous Electronic Transitions; Methods
of Studying Electronic Structure at Very High Pressure: Shifts of
Energy Levels with Pressure; Electronic Transitions in Metats and
Insulator-Metal Transitions; Spin Changes in Iron Compounds;
The Reduction of Ferric Iron; Changes of Oxidation State and Spin
State; Reactions in Aromatic Molecules and Complexes.
1973, 240 x 159 mm, 240 pages, 163 line figures, 2 halftone figures

Chemical Applications of Mclecular Beam

Scattering
M.A. D. Fluendy and K. P. Lawley
Within the past decade, molecular beam scattering techniques have
made an exciting contribution to chemical kinetics and have
revolutionised the determination of intermolecular forces. This book
provides the first unified and reasonably complete account of the
techniques at,a level primarily suited to the needs of the graduate
student and research worker, but comprehensible to undergrad-
uatesin their final year.
The method is unique in that single molecular collisions are
examined and, in principle, complete information about the
encounter can be obtained. The beck introduces the classical and
quantum theory of collisions—relatively unfamiliar to chemists—
befare going on to analyse results. The emphasis throughout is on
tie beam approach to molecular dynamics and the contrast with -
conventional metineds,

CONTENTS: Introduction; Classical Mechanics of Molecular

Scattering; Molecular Beam Sources; Energy and State Selection:
Detection and Measurement; Quantum Mechanics of Scattering;
Elastic Scattering; Reactive Scattering; Inelastic Scattering.
1973, 240x159 mm, 388 pages, 160 line figures

Chapman and Hall

11 New Fetter Lane London EC4P 4EE