FIG. 2 .

One of the first electron diffraction

pictures, which showed the wave nature of
electrons, obtained by G. P. Thomson from
gold foil.

FIG.3. Electron diffraction diagram of a thin chromium film. which was partly polycrystalline
(rings) and partly a single crystal (spots) [I. B. M. Laboratories, Kingston, N.Y.].

and part a compact of tiny crystals. Diffraction patterns have also been
obtained from crystals placed in beams of neutrons or hydrogen atoms, so
that these more massive particles also display wave properties.
Electron beams, owing to their negative charge, have one advantage over
X rays as a means of investigating the fine structure of matter, in that
appropriate arrangements of electric and magnetic fields can be designed
to act as lenses for electrons. These arrangements have been applied in
the development of electron microscopes capable of resolving images as
small as 5 x 10-10 m in diameter. Figure 4. shows an electron microscope
similar to one designed by E. Ruska and B. v. Borries.
Waves and the Uncertainty Principle
The de Broglie wavelengths of ordinary objects are vanishingly
small, and a baseball batter need not consider diffraction phenomena
when he swings at an inside curve.* But in the subatomic world, h/mv is
no longer so small as to be negligible.
The speed of a 1.0g projectile is known to within 1  10-6 ms-1. Calculate the
minimum uncertainty in its position.

Δp=mΔv ( Δv uncertainty in the speed)

1
∵ Δq . Δp≥ ℏ
2

ℏ 1. 055×10−34 Js
Δq= = =5
2mΔv 2×(1. 0×10−3 kg)×(1×10−6 ms−1 )

=5×10−26 (is completely negligible).

 If the mass is that of an electron, then same uncertainty in speed

implies an uncertainty in position far layer than the diameter of an
atom.
 Estimate the minimum uncertainty in the speed of an electron in a
hydrogen atom (taking its diameter as 2a0). [500kms-1]
 FIG 4. Cross-sectional diagram of an electron microscope [Japan Electron
Microscope Company].
The de Broglie wavelengths of electrons are of such a magnitude that
diffraction effects occur in molecules and crystals.
A fundamental tenet of classical mechanics is that it is possible to
measure simultaneously the position and the momentum of any body. The
strict determinism of mechanics rested upon this principle. Knowing the
position and velocity of a particle at any instant and the forces on it at all
times, Newtonian mechanics ventured to predict its position and velocity
at any other time, past or future. Systems were completely reversible in
time, past configurations being obtained simply by substituting —t for t
in the dynamical equations. But, if a particle has some of the properties of
a wave, is it really possible to measure simultaneously its position and its
velocity? The possible methods of measurement must be analyzed before
an answer can be given.
In Fig.5 , suppose a particle of mass m moves along the positive x
direction

FIG. 5 Illustration of the uncertainty

principle by the diffraction of a beam of
particles at a slit. The momentum of the in-
coming beam is all in the x direction. But
as a result of diffraction at the slit, the
diffracted beam has momentum p with
components in both x and y directions.

with a speed v. Its y component of momentum py is known to be zero, but

we do not know anything at all about its coordinate y. At some point x0
we try to measure y by placing in the path of the particle a slit of width
y. Since the particle has wave properties, the wavelength of its de
Broglie wave will be  = h/mv and thus diffraction will occur at the slit.
The form of the diffracted intensity is depicted on the screen placed
beyond x0. From the discussion of Fig.4, we know that the distance
between the first two minima in the diffraction pattern would correspond
to a difference of just one wavelength between the lengths of paths tra-
versed by the waves diffracted from the two edges of the slit. Thus, from
Fig. (5). Δy . sin θ= λ
As a result of the diffraction, the new direction of the momentum cannot
be defined more closely than to within an angular spread ±0, so that, from
2 pλ
Δp y =2 p sinθ=
the figure, Δy

Hence, the product

Δy . Δp y ≈2 pλ=2 h
The product of the uncertainty in the coordinate y times the uncertainty
in its conjugate momentum py is therefore of the order of h. More
precisely,
h 1
Δy . Δp y ≥ = h
4π 2 (46)
where h = h/2.
This is the famous Uncertainty Principle or Principle of Indeterminacy
first stated by Werner Heisenberg in 1926. If we try to define precisely
the position of a particle, we must sacrifice information about its
momentum (or velocity). If we have exact data on its velocity, we cannot
at the same time expect to know exactly where it is located in space.
-The simultaneous determination of velocity, or any related property,
e.g.,energy or momentum, and position is impossible.
Δx . Δv≥h
Δx . ΔP≥h
Δx . ΔE≥h
As an example of (46), consider a microscopic particle 103 nm in
diameter, with a mass of 6  10-13 g. Then
h 6×10−27
Δy . Δv y≈ ≈ −13
≈10−14 cm2 . s−1
m 6×10

If we measured the position to within 1.0 nm, about the resolving power
of an electron microscope, y = 10-7 cm and hence v = 10-7 cm-s-1. With
this indeterminacy in velocity, the position 1 s later would be uncertain to
within 2.0 nm or about 0.2% of the diameter of the particle. Thus, even in
the case of an ordinary microscopic particle, indeterminacy may limit
exact measurements. With particles of atomic or subatomic size, the
effect would be much greater.
When waves are associated with particles, an uncertainty principle
is a necessary consequence. If the wavelength or frequency of an electron
wave is to have a definitely fixed value, the wave must have an infinite
extent. Any attempt to confine a wave within boundaries requires
destructive interference at the boundaries to reduce the amplitudes there
to zero. It follows that an electron wave of perfectly fixed frequency, or
momentum, must be infinitely extended and therefore must have a
completely indeterminate position. To fix the position, we require
superimposed waves of different frequencies, and thus as the position
becomes more closely defined, the frequency and hence the momentum
become less precisely specified.*
The uncertainty relation of (46) can be expressed also in terms of energy
and time. Thus,
h
ΔE . Δt≥
4π (47)

To measure the energy of a system with an accuracy E, the

measurement must be-extended over a period of time of order of
magnitude h/E. This equation is used to estimate the sharpness of
spectral lines. In general, lines arising from transitions from the ground
state of an atom are sharp, because the optical electron spends a long time
t in the ground state and E, the uncertainty in the energy level, is
correspondingly small. The line breadth is related to E by v = E/h.
The lifetime of excited states may sometimes be very short and
transitions between such states give rise to diffuse lines as a result of the
indeterminacy of the energy levels.
The Compton Effect 1923:
Photon collides with an electron increase in  (energy consumed is
overcoming the binding energy).
- The change in  =  does not depend on the nature of the
substance or the wave length of the original radiation and depends
of .
- Elastic collision between photon and electron ; in which the laws of
'
conservation of energy and impulse (momentum) are observed (h v
'
and h v / c are the energy and momentum of scattered electron)
P 2e m2e c 2 1
E= = = me c 2
electron 2 me 2 me 2 (1)
'
photon ΔE=E 2−E 1=h v −hv=−hΔv (2)

from eqn (1) and (2) P2e =−2 meh Δv (3)

- Law of conservation of momentum, the sum of vectors of the
momenta of the scattered photon and recoil electron is equal to the
momenta of the original photon
P ph =P ph cos ψ + Pe cos θ
2
1
1 ix −ix
Pe cos θ=P ph −P ph cos ψ
sin x= ( e −e )
Or 1 2
2i

if θ=zero , cos θ=1 and therefore , 1 ix −ix

cos x= (e +e )
Pe =P ph −P ph cos ψ
2
1 2 (3)
Applying the cosine theorem:
P2e =P2ph1 + P 2ph 2 −2 P2ph 1 P2ph 2 cos ψ
(4)

2 2
P ph1 =P ph2
Incident reflected (5)

∴ P2e =2 P2ph1 −2 P2ph2 cos ψ=2 P2ph1 (1−cos ψ )

(6)
From equations (3) and (6)
2
−2 me hΔv=2 P ph1 (a−cos ψ )
2
P ph1
∴− Δυ= ( 1−cos ψ )
me h (7)
But
(1−cos ψ )=2 sin2 ψ /2 (8)

2
2 P ph
1 2
∴− Δυ= sin ψ / 2
me h (9)

sin2 ψ /2=(0 ,1 ,−1 ) if ψ=θ , v ,3 v)

∴− Δυ=(0 ,1 ,−1)
h hυ c
P= = , υ=
Photon its momentum λ c λ
∂υ c e
∴ =− 2 or dυ=− 2 ∂ λ
∂λ λ λ (10)
From eq (9)
2 P2ph1
c
(
− 2 ∂λ =
λ )
me h
sin 2 ψ / 2
(11)
But
hc 2 h2
P ph = →P ph = 2
1 λc 1
λ (12)
Subst, in eq (11)
c 2 h2
2
∂ λ= 2 sin2 ψ / 2
λ λ me h

2h
∴ ∂ λ= sin2 ψ /2
me c (13)
∂ λ=2 λ o sin 2 ψ /2 (14)
Where
 h
λ o= =0 . 0242 A o =
me c comptom wave length
∂ λ= λ' −λ = reflected – incident radiation.
0 I sindependent of wave length of ineident radiation (photons) or of
nature of scatterer (matter).

ATOMIC ORBITALS
.1. The Schrodinger wave equation
BEFORE we can profitably discuss the behavior of electrons in a molecule,
we must understand their behavior in isolated atoms. This is important
partly because molecules are built out of atoms, but also because many of
the principles which are used in atomic structure apply equally well to
molecular structure. There is an advantage in dealing first with atoms. For
on account of the single nuclear centre of force, there is an added
simplicity not found in molecules where it is of the very essence of the
problem that two or more nuclear centres are involved.
The physical picture of an atom that we use is the familiar Rutherford-
Bohr one in which the appropriate number of electrons move in orbits
around a central nucleus, which we may take to be effectively fixed. In
Bohr's early calculations it was supposed that each electron moved in
some definite orbit though the orbits slightly disturbed each other on
account of the mutual Coulomb repulsion between like charges. Precisely
similar conditions are met with in our solar system (except that all the
Coulomb forces are attractive), so that this picture could properly be
called the planetary atom. However, there are two fundamental objections
to this theory when applied to atoms, objections which do not hold when
applied to planets. These are the presuppositions
(i) that we are able to define the position and velocity of each
electron,
(ii) that, at least in principle, we can follow the motion, or orbit, of each
individual electron, just as astronomers follow the motion of each
individual planet.
In fact, neither of these presuppositions is valid. For, as Heisenberg
showed in 1927 with his Uncertainty Principle, our knowledge of the
behavior of so minute a particle as an electron can never be as precise as
this theory requires. For example, there is no way of measuring exactly
the velocity of an electron in an atom, nor is there any way of locating it
exactly at any given moment. Indeed, the more closely we attempt to
measure its position, the less accurately shall we be able to
simultaneously measure its velocity: and vice versa. If this is so, we have
no right to use such language to describe an atom and we must abandon
the hopeless task of trying to follow an electron in its orbit. We must look
for some alternative description more in keeping with the kind of
information that can be obtained experimentally. Such an alternative
description is provided by the wave mechanics with which this book is
primarily concerned. This theory, introduced in 1926 by Erwin
Schrodinger, rests upon two main lines of evidence. These are:
(i) the wave-character of an electron,
(ii) the probability, or statistical, character of our knowledge. It is
necessary to say a few words about both of these.
The Newtonian, or classical, description of an electron is that it is a point
particle completely defined by its coordinates x, y, z. Its motion, or orbit,
in an atom is then described by the way in which x, y, z vary with the
time. But as early as 1924 de Broglie had shown from some theoretical
considerations involving the invariance of certain relativistic formulae,
that it was possible to associate waves with a moving particle, and that
their wavelength A would be inversely proportional to the momentum p.
The « significance of these waves remained obscure until Davisson and
Germer in 1927 and independently G. P. Thomson in 1928 showed that a
beam of electrons did indeed behave just as if it were a wave and could
be diffracted by a suitable grating (here the regular atomic spacing in a
crystal). Further the wavelength X was exactly that which was predicted
by the de Broglie relation

 = h/p, (1)

where h is Planck's constant. Except at very high velocities p = mv, where

m and v are the mass and velocity of the electron, so that approximately

 = h/mv. (2)

This relation holds for heavier particles also, though on account of their
greater mass,  becomes so small that there is more difficulty in
discovering phenomena where the wave-character is important.
Now if there are waves, there must be a wave equation to describe them.
This is true for light waves, sound waves, water waves, string waves, etc.:
it must also be true for electron waves (or, as they are often called, de
Broglie waves). And so we are led at once to the Schrodinger Wave
Equation.[We shall have something to say about the mathematics of this
equation in Chapter III; but there is something that can be said
immediately about the interpretation of this equation]. This is related to
the second point (ii) above, i.e. the probability character of our know-
ledge. According to Heisenberg's Uncertainty Principle we can never
know exactly where a particle is; in such cases the best that we can do is
to give the probability that it is in any given region. This means that its
position is defined by a probability function. Such a function will vary
from place to place according to the probability that the particle will be
found in each particular region. If we call this function p(x, y, z), then the
particle is most likely to be found in those regions where p is greatest. In
fact p dxdydz ( p d) is the probability that the particle is in the small
volume dxdydz ( d) surrounding the point x, y, z. For that reason p is
sometimes called the probability density. Since the particle must be
somewhere, the total probability is unity, so that

∫ ρ dτ=1 (2)

This introduction of probability density takes account of the fundamental

law of nature, that our knowledge of the position of a particle can never
be absolute.
We have still to connect our wave equation with the density .
Here we may appeal to the physical interpretations of other equations of
wave motion. It is usually the square of the amplitude of a wave that has
significance, rather than the amplitude itself. For example, in an electric
field where E and H are the electric and magnetic vectors the energy
density is (E2+H2)/8TT; and in a progressive wave along a stretched
string, the total energy is proportional to the square of the amplitude. This
suggests that we should make a similar association for electron waves and
other particle waves. Thus, let the solution of the wave equation for a
single particle be a function which we write (x, y, z) and which we call a
wave function. Then we may anticipate that
ρ( x , y, z) αψ 2 ( x, y , z). (4)
The wave equation itself does not determine  absolutely, for we shall
see later that we may always multiply any one solution by an arbitrary
constant and it still remains a solution of the equation. We generally
choose the constant in such a way that the proportionality in equation (4)
is replaced by an equality:
ρ( x , y, z) =ψ 2 ( x , y , z). (5)

Equation (3) then reads ∫ ψ 2 dτ=1

Such wave functions are said to be normalized. If  is not already
normalized, it may be made so on multiplication by N, where
N −2 =∫ ψ 2 ( x , y, z)dτ .
There are occasions in which  is a complex quantity and then we replace
2 ¿
ψ 2 in the above expressions by |ψ| . An entirely equivalent form is ψψ ,
¿
where ψ is the complex conjugate to ψ ; There is a simple reason why
the square of ψ , and not ψ itself, must be associated with the probability
density. When we solve the wave equation, we usually find some regions
of space in which ψ is positive, and others in which it is negative. But the
probability must always be positive or zero; and we are therefore forced
2
to abandon ψ in favour of ψ when trying to relate the wave function and
the density.
Let us suppose that we want to find the behaviour of a certain
particle moving under the influence of given forces. Our procedure is as
follows:
(i) we write down the wave equation in the form appropriate to the
given conditions;
(ii) we solve this equation to find a wave function ψ (x, y, z);
(iii) the probability density is then
ρ=ψ 2 ( x , y , z).
We shall not go into the details of this technique now, because that will
be the subject-matter of Chapter III. For the present we shall be satisfied
with a qualitative account of the procedure and its results when applied to
the study of atomic structure. The pictorial character of these results can
easily be appreciated before we give the theoretical justification for them.
But before going any further, we must point out one very important factor
that has so far been omitted. The wave equation has an infinite number of
solutions, though by no means all of them correspond to any physical or
chemical reality; we call such solutions unacceptable. Acceptable wave
functions must satisfy certain conditions. In the case of an electron which
is bound to an atom or a molecule we can state that  is to be
everywhere finite, single-valued, and continuous; and its gradient must
also be continuous.

It must also be such that the integral ∫ ψ dτ is finite, so that the wave
2

function may be normalized. These conditions seem very simple and

obvious, but in fact they are very far-reaching in their effects. For the
wave equation contains in one of its terms the total energy E of the
electron, and therefore its solutions themselves depend on E. We have
already stated that only certam of these possible solutions are acceptable
wave functions. This means that it is only for certain values of the energy
that there exist physically significant probability functions. We call these
stationary states since they arise from a constant energy, and in such
2
cases it may be shown that |ψ| is independent of the time. These are the
only states in which we shall be interested. The energies are sometimes
called eigenvalues, and the corresponding wave functions eigenfunctions,
but we shall be content usually to refer to them simply as the allowed
energy levels and wave functions. It was one of the major triumphs of the
wave equation that the existence of discrete energy levels followed
inevitably, without the need to introduce certain quantum conditions, as
Bohr had been compelled to do in his earlier theory. If we may
anticipate.
We know that H atom, ground state

a 0=h2 /4 π 2 me 2 =0 .52 g×10−8 cm (1)

−2 π 2 me 4 −e 2
E= = =−13 . 60 eV
h2 2 a0 (2)
This electron is described by a suitable wave function:

ψ=
√ 1 −r/a 0
πa 30
e
(4)

Where r is the distance from the origin. The propability density

1 −r /a0
ρ= e
πa30 (5)
It will be noticed at once that the motion takes place in three dimensions and
that  is sphenically symmetrical around the origin. Further, the wave
function (4) is already notmalized since:
ϕ ϕ
−2 r/a 0
∫ ψ 2 dt=∫ ψ 2 4 πr2 dr=∫ ψa−30 r2 e dr =1
0 0 (6)
1 ix −ix
sin x= (e −e )
2i

1 ix −ix
cos x= (e +e )
2
Atomic orbitats :

The wave function

ψ=
√ 1 −r/ a 0
πa 30
e
where r is the distance from the
2 2 2
origin, a0 = Bohr radius = h / 4 π me .
 1 −r /a0
ρ= e
πa30

The Physical picture of an atom Ruther ford-Bohr

Two Fundamental Objections:
i- That we are able to define the position and the velocity of each
electron.
ii- That at last in principle, we ean follow the motion, or orbit, of
each individual electron.
- Heisenberg 1927 uneertainty Principle.
- Experimental foundation Deality between mass and wave
- De Broglic relation  = h/p (1)

Erwin Schrödinger, rests upon two main lines of evidence

i- the wave character of an electron.
ii- The probability, or statistical, characture of owr knowledge.

Now if there are waves, there must be a wave equation to describe

then. This is true for light waves, sound waves, water waves, string
waves, etc. : it must be also true for electron waves.
According to Heisenzerg's principle we can never know exactly
where a particle is ; in such cases the best that we can do is to give the
probability that it is in any given region i.e. its position is defined lay a
probability function. Such a function will wary from place to place
according to the probability that the particle will be found in each
particular region.

If we call this function (x, y, z), then ∫ ρ dτ=1 (2)

 = probability density .
 We have still to connect our wave equation with the density .

ρ( x , y, z)αψ 2 ( x, y , z ) (3)
ψ 2 = square of the amphitude

If ρ( x , y , z)=ψ 2 ( x , y , z) (4)

∴∫ v 2 dτ =1 (5)
Normalized. If Not
N −2 =∫ ψ 2 ( x , y, z)dτ (6)

2
Why the ψ and not ? ψ = values
A little, it was particularly gratifying to discover that in the case of the
hydrogen atom, where in fact Bohr's theory gave energy levels in
agreement with experiment, the new theory gave exactly the same
agreement; and in the case of the helium atom, where Bohr's theory gave
wrong energy values, the new theory gave energies as accurate as they
could be measured experimentally. It is in this sense that we may say that
the wave equation has been 'proved'.
2.2. The charge-cloud interpretation of 
According to the wave equation a moving particle is represented-
by a wave function  such that 2d is the probability that it is found in
the volume d. There is, however an alternative and more pictorial
(though less strictly accurate) interpretation of  which may be given as
follows. Let us deal with the case in which the moving particle is an
electron. Then we suppose that this electron is spread out in the form of a
cloud —we refer to it as a charge-cloud—the density of this cloud at any
point being proportional to 2. In places where 2 is largest, the charge-
cloud is densest and most of the negative charge is to be found.
The essential difference between this interpretation and our earlier
one is that instead of speaking of the probability density (i.e. the chance
of finding the electron in any given region) we speak of the actual particle
density. Now if a single electron is a particle, it cannot possibly be
distributed over regions of the size of an atom or molecule, which are of
the order of 10-8 cm in each direction, so that the charge-cloud picture,
though very useful, is not strictly correct. Only the statistical, or
probability, interpretation is really valid. A link between the two
viewpoints may be found in the following way: let us suppose that at a
particular moment we were able by some means to determine exactly
where the electron was, and that we represented this position by a minute
dot in a space of three dimensions. J «et us now repeat the observation a
very large number of times (perhaps a million times) and put a similar dot
in the appropriate place in this space. If the dots arc so small that we
cannot distinguish individual ones from their neighbors, the general effect
of this diagram will be exactly. The same as a cloud; the densest parts of
the cloud will be those where there arc most dots, and those are precisely
the places where our individual observations arc most likely to discover
the electron. So the density of the charge-cloud is a direct in measure of
the probability function.
Despite its lack of validity we shall find the idea; of a charge-cloud most
useful, and shall frequently employ it. For example, the wave functions of
an electron in an atom are not strictly confined, but  stretches to infinite
distance from the nucleus. This implies that there is a finite chance of
finding the electron even at large distances. This chance is very small n'
the distance exceeds about 2 or 3 x l0-8 cm, so that not much significance
attaches to that part of the probability outside a certain region. Using the
charge-cloud picture we might say that there is a certain contours for each
ψ such that 90 percent, (or if we wish, 99 percent.) of the charge lies
within this contour. We shall shortly describe some typical contours and
find characteristic patterns. We could refer to one of those as the
boundary surface for an electron in this allowed stationary state. The
significance of the shape of the various boundary surfaces can hardly be
exaggerated; for we shall see later that those shapes largely determine the
stereo chemical disposition of the atoms in a polyatomic molecule.
2.3. Hydrogen atom, ground state
The ideas that we have just boon describing are very nicely illus-
trated by the example of the ground state of the hydrogen atom. We have
only one electron to deal, with, and this moves round the nucleus which
we may bake to be fixed at the origin of coordinates. In such a case there
arc many allowed wave functions and corresponding energies; the lowest
of these is called the ground state.
According to the Bohr Theory the electron moves round the
nucleus in a circle whose radius is called the radius of the lust orbit, or
more simply 'the Bohr radius', and which is written a0. It is found that this
radius is related to the mass m and. charge e of the electron by the

formula a 0=h2 /4 π 2 me 2 =0 .520×10−8 cm. (6a)

Similarly the allowed energy is
2 π 2 me 4 e2
E=− =− =−13 .60 eV .
h2 2 a0 (6b)
The minus sign here means that this is the energy, or work, that we have
to do in order to separate the proton and the electron to infinite distance
apart. The whole of the motion takes place in one plane.
But according to the wave mechanical theory tins electron is described by
a suitable wave function. It is found that:
 ψ=
√( πa30)
1 −r/ a 0
e ,
(7)
where r is the distance from the origin. From this it follows that the
probability density is
1 −2r / a 0
ρ= e .
πa30 (8)
It will be noticed at once that the motion takes place in three
dimensions, and that p is spherically symmetrical around the origin.
Further, the wave function (7) is already normalized since
∞ ∞
−2r /a 0
∫ψ 2
dτ=∫ ψ 4 πr dr=∫ 4a−3
2 2
0 r dr =1
0 0

There are several ways in which we can exhibit graphically the nature of
(7) or (8). We could for example:
2
(a) plot a graph showing how ψ and ψ (≡ρ ) vary with r;
(b) draw contours of constant value of ψ . In this case the contours are
concentric spheres, and at all points on any one sphere ψ has the same
value;
(c) draw the charge-cloud (or, in this case, a section of it by some plane
through the origin);
(d) draw the boundary surface. This is that particular one of the contours
referred to in (b) such that the total charge outside the contour is some
definite small percentage (e.g. 10 per cent.) of the total electronic
charge. All these possibilities pro illustrated in Fig. 2.1. Of these
diagrams (a) and (b) are very detailed, and require an exact knowledge
of  ; (c) is able to give us a very good general impression of the
charge distribution even if we are not able to represent the density
 FIG. 2.1. Representation of the wave function for Uio groxmd stalo of a
hydrogen atom.
(a) graph of  and  .2
(c) charge-cloud.
1
3 −
πa
(b) contour of  (uuitra of ( 0 ) 2 ). (d') boundary surface.
of the cloud "with complete precision; (d) is much the simplest, but
for many purposes it provides a surprisingly adequate pictorial
representation, and Ave shall make frequent use of it.
There is yet another method of representing the charge density
which is often used for atoms. Since the atom is spherically sym-
metrical  is here a function only of the radial distance r. So,
Instead of plotting the density (r), we plot what is called the radial
density 4 r2(r). Since 4 r2dr is the volume lying between the two
spheres r, r+dr, it follows that 4 r2(r) dr is the total probability that the
electron is at a distance between r and r + dr of the origin. Fig. 2 shows
the graph of tins radial density. It is interesting, by way of a final
comparison with the Bohr theory, that the maximum radial density in the
new theory occurs when r = a0, so that in this case the most probable
distance of the

FIG. 2.2. (a) Radial distribution function or density f >r the ground state of
hydrogen. (6) Fraction of charge-cloud outside a sphere of radius r for
the ground state of atomic hydrogen.

electron from the nucleus is precisely that which it is supposed to

have permanently in the old theory.
On the riffht-hand side of Fig. 2 there is shown the variation of
P(r), where P(r) is that fraction of the total charge-cloud which lies
outside a sphere of radius r. Evidently P(0) = 1, and P() == 0. It
will be noticed that P(r) falls off rapidly with r. If, for example in (d)
above, we chose the boundary surface for which 1.0 per cent, of the
charge lay outside, its radius would be 2.6a0 = 1.4 A. The analytical
expression for P(r) is
 { }
∞
−2 r/a 0 2 r 2r 2
P(r )=∫ ψ 2 4 πr 2 dr=e 1+ +
r a0 a20

2.4. Atomic Orbitals

The wave function (7) may be said to describe tlio motion of the
electron. In a rather loose way we could speak of it as describing the
orbit, though of course we hav now abandoned the hopeless attempt to
follow the electron in its path; in fact wo believe that even the idea of a
path has NO meaning. But on account of its relationship to the distribution
of the electron we call it an atomic orbital. It will, be convenient to
abbreviate this to a.o.
The a.o. drawn in Figs. 1 and 2 is not the only one for hydrogen. It
is the ground state orbital and for that reason it is the most important one
chemically, since an atom is normally in its state of lowest energy.
However, there are plenty of other allowed energies and corresponding
wave functions. Fig. 3 shows some of the more frequently used a.o.'s,
including our previous one, now referred to under its spectroscopic name
of Is. It is absolutely essential to have a clear mental picture of the more
common a.o.'s, and in particular, to recognize and remember their
symmetry properties.
For this purpose the most significant classification is into the types
s, p, d,...} examples of which, arc shown in Fig. 3. s-type a.o.'s are all
spherically symmetrical so that the charge-cloud density is a function
only of r. All the oilier types are unsym-mctrical. For example, there are
three p-type a.o.'s in which the boundary surface consists of two regions
together resembling a 'dumb-bel'. If we exclude that part of the electron-
cloud which is very near the origin, and not effective in molecular
formation, then in one half of the dumb-bell  is positive and in the other
it is negative. There is a very marked directional character in these
orbital's, which, we exhibit by means of a suffix px, py, pz. Fig. 4 shows
approximate boundary surfaces for these a.o.'s; each of them is
symmetrical around the direction shown by its suffix. These three p-type
orbital's are entirely equivalent except for their directions, and they are all
linearly independent. There arc only three such, which are linearly
independent. This means that any other similar jp-type orbit which points
in a different direction can be regarded as the superposition of certain
amounts of the three basic ones. In actual fact, the resolution is exactly
Analogous to the resolution of a vector into it: three components in
mutually perpendicular directions. THUS, if l,m, n denote the direction
cosines of the direction in which the additional dumb-bell is to point, its
wave function is (plmn)t where in an obvious notation
 (plmn) = l{Px)+mp(py)+ n (Pz' (9)
We shall require this formula later on.
An important characteristic of these a.o.'s is that the regions
FIG. 2.3. Some atomic orbital's for hydrogen.
 Where  is of opposite sign are separated by a 'nodal plane', over
which  = 0. For example, in the orbital px, this is the plane x = 0, a fact
which is obvious at once if we are told that for px- type a. o.,

 (px) = x  some function of r.

(10)

FIG. 2.4. Typos of atomic orbital; approximate boundary surfaces.

It is convenient, when drawing the boundary surface, to insert ±

signs, as in Fig. 4, in those regions where  is positive or negative.