UNIT 3

Lattice vibrations and Phonons

• Concept of lattice mode of vibration
• Elastic vibrations of continuous media
• Phase velocity
• Group velocity
• Vibrations of one dimension monoatomic linear
lattice
• Vibrations of one dimension diatomic linear lattice
Phonons –momentum
• Inelastic scattering of photons by phonons
• Inelastic scattering of X rays by photons
• Inelastic scattering of neutrons by phonons
 Lattice Dynamics
related to movement of atoms determined by electronic structure
about their equilibrium positions

Physical properties of solids

•Sound velocity

•Thermal properties: -specific heat

-thermal expansion
-thermal conductivity
(for semiconductors)

•Hardness of perfect single crystals

(without defects)
Lattice dynamics above T=0
•Crystal lattices at zero temperature posses long range order – translational
symmetry (e.g., generates sharp diffraction pattern, Bloch states, …).
•At T>0 ions vibrate with an amplitude that depends on temperature – because
of lattice symmetries, thermal vibrations can be analyzed in terms of collective
motion of ions which can be populated and excited just like electrons – unlike
electrons, phonons are bosons.
Thermal lattice vibrations are responsible for:

→ Thermal conductivity of insulators is due to dispersive

lattice vibrations (e.g., thermal conductivity of diamond is 6 times larger
than that of metallic copper).
→ They reduce intensities of diffraction spots and allow for
inellastic scattering where the energy of the scatter (e.g., neutron)
changes due to absorption or creation of a phonon in the target.
→ Electron-phonon interactions renormalize the properties of
electrons (electrons become heavier).
→ Superconductivity (conventional BCS) arises from multiple
electron-phonon scattering between time-reversed electrons.

4
Thermal Energy & Lattice Vibrations

The atoms in a crystal vibrate about their equilibrium positions.

This motion produces vibrational
waves.

The amplitude of this vibrational motion increases

as the temperature increases.

In a solid, the energy associated with these vibrations is called

Thermal
Energy
• A knowledge of the thermal energy is fundamental to obtaining an
understanding many of the basic properties of solids . A relevant
question is how do we calculate this thermal energy?
• Also, we would like to know how much thermal energy is available to
scatter a conduction electron in a metal or semiconductor. This is
important; this scattering contributes to electrical resistance in the material.
• Most important, though, this thermal energy plays a fundamental
role in determining the
Thermal Properties of a Solid
• A knowledge of how the thermal energy changes with temperature gives
an understanding of the heat energy which is necessary to raise the
temperature of the material.
• An important, measureable property of a solid is it’s

Specific Heat or Heat Capacity

 Lattice Vibrational Contribution to the Heat Capacity
The thermal energy is the dominant contribution to the heat
capacity in most solids. In non-magnetic insulators, it is the only
contribution. Some other contributions:
Conduction Electrons in metals & semiconductors.
The magnetic ordering in magnetic materials.
Calculation of the vibrational contribution to the thermal energy & heat
capacity of a solid has 2 parts:
1. Evaluation of the contribution of a single vibrational mode.
2. Summation over the frequency distribution of the modes.
 Uniform Solid Material

There is energy associated

with the vibrations of atoms.

They are tied together with

bonds, so they can't vibrate
independently.

(X-1) (X) (X+1)

 Uniform Solid Material

There is energy associated

with the vibrations of atoms.

They are tied together with

bonds, so they can't vibrate
independently.

The vibrations take the form

of collective modes which (X-1) (X) (X+1)

propagate through the

material.
 SOUND WAVES
• Mechanical waves are waves which propagate through a material
medium (solid, liquid, or gas) at a wave speed which depends on
the elastic and inertial properties of that medium. There are two
basic types of wave motion for mechanical waves: longitudinal
waves and transverse waves.

Longitudinal Waves

Transverse Waves
 Three Dimensions
For each mode in a given propagation direction,
the dispersion relation yields acoustic and optical
branches:
• Acoustic
• Longitudinal (LA)
• Transverse (TA)
• Optical
• Longitudinal (LO)
• Transverse (TO)
NaCl – two atoms per
If there are p atoms in the primitive cell, there primitive cell
are 3p branches in the dispersion relation: 3 6 branches:
acoustic and 3p -3 optical.
1 LA
1 LO
2 TA
2 TO
 Acoustic & Optic Branches
• Despite the fact that diatomic chain model is one-dimensional, it’s
results for the vibrational normal modes ω
contain considerable qualitative physics that
carries over to the observed vibrational
frequencies for many real materials.
• So, much of the physics contained in the diatomic chain results can
teach us something about the physics contained in the normal
modes of many real materials.
• In particular, ALL MATERIALS with 2 atoms per unit cell
are observed to have two very different
kinds of vibrational normal modes.
These are called The
Acoustic Branch & The Optic Branch
 The Acoustic Branch
• This branch received it’s name because it contains long wavelength
vibrations of the form ω = vsk, where vs is the velocity of sound. Thus,
at long wavelengths, it’s ω vs. k relationship is identical to that for
ordinary acoustic (sound) waves in a medium like air.
The Optic Branch
• This branch is always at much higher vibrational frequencies than the
acoustic branch. So, in real materials, a probe at optical frequencies is
needed to excite these modes.
• Historically, the term “Optic” came from how these modes were
discovered. Consider an ionic crystal in which atom 1 has a positive
charge & atom 2 has a negative charge. As we’ve seen, in those modes, these
atoms are moving in opposite directions. (So, each unit cell contains an oscillating
dipole.) These modes can be excited with optical frequency range electromagnetic
radiation.
 A Longitudinal Optic Mode

The vibrational amplitude is highly exaggerated!

 A Transverse Optic Mode
for the Diatomic Chain

The vibrational amplitude is highly exaggerated!

For the case in which
the lattice has some
ionic character, with
+ & - charges alternating:
 A Long Wavelength Longitudinal
Acoustic Mode

The vibrational amplitude is highly exaggerated!

 A Short Wavelength Longitudinal
Acoustic Mode

The vibrational amplitude is highly exaggerated!

 A Transverse Acoustic Mode
for the Diatomic Chain

The vibrational amplitude is highly exaggerated!

For the case in which

the lattice has some
ionic character, with
+ & - charges alternating:
 Acoustic vs. Optic Phonons
Which has lower energy? Why?

Acoustic Mode Optic Mode

Lower Energy
Less Compression of Springs
 What is a phonon?

• Consider the regular lattice of atoms in a uniform solid

material.
• There should be energy associated with the vibrations of these
atoms.
• But they are tied together with bonds, so they can't vibrate
independently.
• The vibrations take the form of collective modes which
propagate through the material.
• Such propagating lattice vibrations can be considered to be
sound waves.
• And their propagation speed is the speed of sound in the
material.
What is a Phonon?
• We’ve seen that the physics of lattice vibrations in a crystalline solid
reduces to a CLASSICAL normal mode problem.
The goal of the entire discussion has been to
find the normal mode vibrational frequencies of the solid.
• In the harmonic approximation, this is achieved by first writing the
solid’s vibrational energy as a system of coupled simple harmonic
oscillators & then finding the classical normal mode frequencies & ion
displacements for that system.
• Given the results of these classical normal mode calculations for
the vibrating solid, in order to treat some properties of the solid,
it is necessary to QUANTIZE these normal modes.
• These quantized normal modes of vibration are called
PHONONS
• PHONONS are massless quantum mechanical particles which
have no classical analogue.
– They behave like particles in momentum space or k space.
• Phonons are one example of many like this in many areas of physics. Such
quantum mechanical particles are often called
“Quasiparticles”
Examples of other Quasiparticles:
Photons: Quantized Normal Modes of electromagnetic waves.
Rotons: Quantized Normal Modes of molecular rotational excitations.
Magnons: Quantized Normal Modes of magnetic excitations in magnetic solids
Excitons: Quantized Normal Modes of electron-hole pairs
Polaritons: Quantized Normal Modes of electric polarization excitations in solids
+ Many Others!!!
 Comparison of Phonons & Photons
PHONONS
• Quantized normal modes of lattice vibrations.
PHOTONS
The energies & momenta of phonons are • Quantized normal modes of
quantized
electromagnetic waves. The
energies & momenta of photons
are quantized
h s hc
E phonon  E photon 
 
h h
p phonon  p photon 
 
Phonon wavelength: Photon wavelength (visible):
λphonon ≈ a0 ≈ 10-10 m λphoton ≈ 10-6 m
 Wave-Particle Duality
ee n
be s
like to
d on’t
y
The ther 
toge

Just as light is a wave motion that is considered as composed of

particles called photons, we can think of the normal modes of vibration
in a solid as being particle-like.

Quanta of lattice vibration is called the phonon.

 Phonon:
A Lump of Vibrational Energy
Propagating lattice vibrations can be considered to be
sound waves, and their propagation speed is the
speed of sound in the material.

Phonon:
Sound
Wavepackets
 Phonon:
A Lump of Vibrational Energy
Propagating lattice vibrations can be considered to be
sound waves, and their propagation speed is the
speed of sound in the material.
Roughly how big is ?
Phonon:
Sound
Wavepackets
 Phonon:
A Lump of Vibrational Energy
Propagating lattice vibrations can be considered to be
sound waves, and their propagation speed is the
speed of sound in the material.
Roughly how big is ?
Phonon:
Sound
Wavepackets The different possible
oscillations are limited

by the size of the system.

Crystals are big! Result?

Reminder to the physics of oscillations and waves
(a few slides)

Harmonic oscillator in classical mechanics

Example: vertical springs

Reminder to the physics of oscillations and waves
(a few slides)

Harmonic oscillator in classical mechanics

Hooke’s law

Example: vertical springs

Cx
 Reminder to the physics of oscillations and waves
(a few slides)

Harmonic oscillator in classical mechanics

Hooke’s law

Example: vertical springs

Cx

Epot = ½ Cx2

x
 Reminder to the physics of oscillations and waves
(a few slides)

Harmonic oscillator in classical mechanics Equation of motion:

m x  Fspring
Hooke’s law

Example: vertical springs

Cx

Epot = ½ Cx2

x
 Reminder to the physics of oscillations and waves
(a few slides)

Harmonic oscillator in classical mechanics Equation of motion:

m x  Fspring
x  C
K~
Hooke’s law

Example: vertical springs Cxx  0 or ~

m x  K x 0
where m
x( t )  Re(~
x( t ))

Cx

Epot = ½ Cx2

x
 Reminder to the physics of oscillations and waves
(a few slides)

Harmonic oscillator in classical mechanics Equation of motion:

m x  Fspring
x  C
K~
Hooke’s law

Example: vertical springs Cxx  0 or ~

m x  K x 0
where m
x( t )  Re( ~
x( t ))
~
Solution with ~
x( t )  A ei  t
x( t )  A cos( t  )
where 
K
m
Cx

Epot = ½ Cx2 X=A cos ωt

x
Traveling plane waves:
Traveling plane waves:
Y

X
Traveling plane waves:
Y

X
 Displacement as a function of time and k
Traveling plane waves:
Y y (t )  A cos (kx  t )
or
~ ~ i ( kx t )
y (t )  A e
X (Phonon wave vector also often given
as q or K instead of k)
 Displacement as a function of time and k
Traveling plane waves:
Y y (t )  A cos (kx  t )
or
~ ~ i ( kx t )
y (t )  A e
X (Phonon wave vector also often given
as q or K instead of k)

Useful to mention where approach not necessary

Consider a particular state of oscillation (long )
Yconstant
 Displacement as a function of time and k
Traveling plane waves:
Y y (t )  A cos (kx  t )
or
~ ~ i ( kx t )
y (t )  A e
X (Phonon wave vector also often given
as q or K instead of k)

Useful to mention where approach not necessary

Consider a particular state of oscillation (long )
Yconstant

d
kx  t   d const.  0
dt dt
 Displacement as a function of time and k
Traveling plane waves:
Y y (t )  A cos (kx  t )
or
~ ~ i ( kx t )
y (t )  A e
X (Phonon wave vector also often given
as q or K instead of k)

Useful to mention where approach not necessary

Consider a particular state of oscillation (long )
Yconstant

d
kx  t   d const.  0
dt dt

x  v 
k
> interatomic spacing continuum approach fails
Hooke's Law

• One of the properties of elasticity is that it takes about twice as much

force to stretch a spring twice as far. That linear dependence of
displacement upon stretching force is called Hooke's law.

It takes twice
as much force
Fspring  k .x to stretch a
spring twice

Spring constant k
F as far.

2F 
SOUND WAVES

• Sound waves propagate through solids. This tells us that wavelike

lattice vibrations of wavelength long compared to the interatomic
spacing are possible. The detailed atomic structure is unimportant for
these waves and their propagation is governed by the macroscopic
elastic properties of the crystal.

• We discuss sound waves since they must correspond to the low

frequency, long wavelength limit of the more general lattice
vibrations considered later in this chapter.

• At a given frequency and in a given direction in a crystal it is possible

to transmit three sound waves, differing in their direction of
polarization and in general also in their velocity.
Quantization of Elastic Waves
The energy of an elastic mode of angular frequency 
is
En   n  1
 
 2

It is quantized, in the form of phonons, similar to the

quantization of light, as both are derived from a
discrete harmonic oscillator model.

Elastic waves in crystals are made up of phonons.
Thermal vibrations are thermally excited phonons.
Normal Modes of Vibration
One dimensional model # 1: The Monatomic Chain
• Consider a
Monatomic Chain of
Identical Atoms
with nearest-neighbor,
“Hooke’s Law”
type forces (F = - Kx) between the atoms.
• This is equivalent to a force-spring model,
with masses m & spring constants K.
 One Dimensional Model # 1:
The Monatomic Chain
• This is the simplest possible solid.
• Assume that the chain contains a very large number
(N  ) of atoms with identical masses m. Let the
atomic separation be a distance a.
• Assume that the atoms move only in a direction parallel
to the chain.
• Assume that only nearest-neighbors interact with each
other (the forces are short-ranged).
a a a a a a

Un-2 Un-1 Un Un+1 Un+2

• Consider the simple case of a
monatomic linear chain with only
nearest-neighbor interactions.
• Expand the energy near the a
a
equilibrium point for the nth atom.
Then, the
Newton’s 2 nd
Law 0

equation of motion becomes:

Un-1 Un Un+1

..
This can be seen as follows.
The total force on the nth
atom is the sum of 2 forces: a a
The force to the right is: .
K (u n 1  u n )
The force to the left is: mun  C(2un  un1  un1)  0
Un-1 Un Un+1

K (u n  u n 1 )
Total Force = Force to the right – Force to the left
..
The Equation of Motion of each atom is of
this form.Only the value of ‘n’ changes.
• Assume that all atoms oscillate with the same amplitude
A & the same frequency ω. Assume harmonic solutions
for the displacements un of the form:
un  A exp i  kx  t 
dun
 i A exp i  kxn0  t 
.
0
n un 
dt
d 2 un ..
u n  2   i   2 A exp i  kxn0  t 
..
2

dt u n   un 2

Undisplaced 0 Displaced
xn  na xn  na  un
Position: Position:
• Put all of this into the equation of motion:
..

• Now, carry out some simple math manipulation:

 Equation of Motion for the nth Atom
..
mu n  K (un 1  2un  un 1 )

2
 m A e

i kxn0 t 
 K Ae 
i kxn 10 t 
 2A e

i kxn0 t 
 Ae

i kxn 10 t 

k ( n  1) a kna k ( n  1) a
kna
2 i  kna t 
 m A e  K Ae 
i  kna  ka t 
 2A e
i kna t 
 Ae
i kna  ka t 

2
 m A e
i  kna t 
 K Ae  i  kna t 
e
ika
 2A e
i kna t 
 Ae
i kna t 
e
 ika

Cancel Common Terms & Get:
 m 2  K  eika  2  e ika 
• Mathematical Manipulation finally gives:

• After more manipulation, this simplifies to

Solution to the Normal
Mode Eigenvalue Problem
for the monatomic chain.

• The maximum allowed frequency is:

• The physical significance of these results is that, for the

monatomic chain, the only allowed vibrational frequencies ω must
be related to the wavenumber k = (2π/λ) or the wavelength λ in this way.

• This result is often called the “Phonon Dispersion Relation” for

the chain, even though these are classical lattice vibrations &
there are no (quantum mechanical) phonons in the classical theory.
 “Phonon Dispersion Relations” or Normal Mode
Frequencies or ω versus k relation for the monatomic chain.
w
K
max  2
m
Vs   / k
C A
B

k
–л/a 0 л/a 2л/a

Because of BZ periodicity with a period of 2π/a, only the first

BZ is needed. Points A, B & C correspond to the same
frequency, so they all have the same instantaneous atomic
displacements.
 Monatomic Chain 4K ka
 sin
Dispersion Relation m 2
Some Physics Discussion
• We started from the Newton’s 2nd Law equations of motion for N
coupled harmonic oscillators. If one atom starts vibrating, it does not
continue with constant amplitude, but transfers energy to the others in a
complicated way. That is, the vibrations of individual atoms are not
simple harmonic because of this exchange of energy among them.
• On the other hand, our solutions represent the oscillations of
N UNCOUPLED simple harmonic oscillators.
• As we already said, these are called the Normal Modes of the
system. They are a collective property of the system as a whole
& not a property of any of the individual atoms. Each mode represented
by ω(k) oscillates independently of the other modes. Also, it can
be shown that the number of modes is the same as the original
number of equations N. Proof of this follows.
To establish which wavenumbers are possible for the
one-dimensional chain, reason as follows: Not all values
are allowed because of periodicity. In particular, the nth
atom is equivalent to the (N+n)th atom. This means that
the assumed solution for the displacements:
un  A exp i  kxn0  t 

must satisfy the periodic boundary condition: un  u N  n

This, in turn requires that there are an integer number of
wavelengths in the chain. So, in the first BZ, there are only N
allowed values of k. Na  p
Na 2 2
Na  p      Nk  p
p k a
• The physical significance of wave numbers k outside of the
First Brillouin Zone [-(π/a)  k  (π/a)]?
• At the Brillouin Zone edge:
• This k value corresponds to the maximum frequency. A detailed
analysis of the displacements shows that, in that mode, every atom
is oscillating π radians out of phase with it’s 2 nearest neighbors.
That is, a wave at this value of k is A STANDING WAVE.

Black: k = π/a
or  = 2a

Green:
k = (0.85)π/a
or  = 2.35 a x
Points A and C have the same frequency
& the same atomic displacements. It can w 2
K
m
be shown that the group velocity Vs   / K

vg = (dω/dk) there is negative, so that C B A

a wave at that ω & that k moves to the
left. -π/a 00 k
π/a 2π/a k
The green curve (below) corresponds to ω(k) (dispersion relation)
point B in the ω(k) diagram. It has the
same frequency & displacement as points Points A & C are symmetrically
A and C, but vg = (dω/dk) there is equivalent; adding a multiple of 2π/a
positive, so that a wave at that ω & that k to k does not change either ω or vg,
moves u
to the right. so point A contains no physical
n
information that is different from
point B.
x
T The points k = ± π/a have special
a  2m  4K sin 2 ka significance
u 2
n n  n2  n 2n 
k a
x
Bragg reflection occurs at k= ± nπ/a
 The Monatomic Chain
k = (/a) = (2/);  = 2a

k  0;   
For visualization purposes, it is
sometimes useful to visualize a
plane of atoms, made up of a
large number of parallel chains
like the one we just analyzed.
See the next few slides:
• Briefly look in more detail at the group velocity, vg.
• The dispersion relation is:
4K ka
 sin
• So, the group velocity is: m 2
vg  (dω/dk) = a(K/m)½cos(½ka)
vg = 0 at the BZ edge [k =  (π/a)]
• This tells us that a wave with λ corresponding to a zone edge
wavenumber k =  (π/a) will not propagate.
That is, it must be a standing wave!
• At the BZ edge, the displacements have the form (for site n):
Un= Uoeinka = Uo ei(nπ/a) = Uo(-1)n
 Group Velocity, vg in the 1st BZ
vg  (dω/dk) At the 1st BZ Edge,
= vg = 0
a(K/m)½cos(½ka) • This means that a wave
with λ corresponding to
a zone edge
wavenumber
k =  (π/a)
Will Not
Propagate!
• That is, it must be a
1st BZ Standing Wave!
One Dimensional Model # 2:
The Diatomic Chain
• Consider a Diatomic Chain of Two Different Atom Types with
nearest-neighbor, Hooke’s Law type forces (F = - kx) between the
atoms. This is equivalent to a force-spring model with two
different types of atoms of masses, M & m connected by identical
springs of spring constant K.
(n-2) (n-1) (n) (n+1) (n+2)
K K K K
M M m M a)
m
a

b)

Un-2 Un-1 Un Un+1 Un+2

• This is the simplest possible model of a diatomic crystal.

• a is the repeat distance, so, the nearest-neighbor separation is (½)a
• This model is complicated due to the presence of 2 different atom
types, which, in general, move in opposite directions.

M m M m M

Un-2 Un-1 Un Un+1 Un+2

• The GOAL is to find the dispersion relation ω(k) for this model.
• There are 2 atom types, with masses M & m, so there will be 2
equations of motion, one for M & one for m.
..
M u n  K (un1  un )  K (un  un1 ) Equation of Motion
 K (un1  2un  un1 ) for M

..
mu n .. K (un  un1 )  K (un1  un2 )
-1
Equation of Motion
mu n  K (un  2un1  un2 ) for m
-1
• As before, assume harmonic (plane wave) solutions for the atomic
displacements Un:

M m M m M

Un-2 Un-1 Un Un+1 Un+2

un  A exp i  kxn0  t  xn0  na / 2 Displacement

for M
un   A exp i  kxn0  t  Displacement
for m
α = complex number which determines the relative amplitude and phase of
the vibrational wave. Put all of this into the two equations of motion.

u n   2 A exp i  kxn0  t 

..
Carry out some simple math
manipulation as follows:
 Equation of Motion for the nth Atom (M)
..
M u n  K (un1  2un  un1 )
 k  n 1a  k  n 1a
 kna
i

t   i

t   kna
i

t  i t  


 2 MAe  K   Ae   2 Ae  2    Ae   
 2  2  2

 
 
 kna
i

t    kna
i

t  i ka
 kna
i

t 
 kna
i t   i ka 


 2 MAe  2 
 K   Ae  2  e 2  2 Ae  2    Ae  2  e 2 
 
 
Cancel Common Terms
 i
ka
i
ka

 M  K   e  2   e 
2 2 2 eix  e  ix  2 cos x
 
 ka 
 2 M  2 K 1   cos 
 2 
 Equation of Motion for the (n-1)th Atom (m)
..
m u n 1  K (un  2un 1  un  2 )
 k  n 1a  k  n 1a  k n  2 a
i

t   i kna t  i

t  i t  


 A 2 me  K  Ae  2   2 Ae   
2 2 2
  
 Ae 
 
 
 kna
i

t   i ka  i kna 
t 
 kna
i

t   i ka
 kna
i

t   i 2 ka 
 mAe 2  2 
e 2
 K  Ae  2   2 Ae  2  e 2  Ae  2  e 2 
 
 
Cancel Common Terms
i
ka
 i
ka
 ika 
 me
2
 K 1  2 e  e 
2 2

 
 ka 
 i
ka
i
ka
  m  2 K  cos   
2
 m  K  e  2  e 
2 2 2
 2 
 
eix  e  ix  2 cos x
• The Equation for M becomes:

(1)
• The Equation for m becomes:

(2)
• (1) & (2) are two coupled, homogeneous, linear
algebraic equations in the 2 unknowns α & ω as
functions of k.
• More algebra gives:   2 K cos( ka / 2) 2 K   2
M

2K   m2
2 K cos( ka / 2)
• Combining (1) & (2) & manipulating:
• Cross multiplying & manipulating with (1) & (2):
2 K cos(ka / 2) 2K   2 M
 
2K   m
2
2 K cos(ka / 2)
ka
4 K cos ( )  4 K 2  2 K  2 ( M  m)   4 Mm
2 2

2
ka
4 K 2 (1  cos 2 ( ))  2 K  2 ( m  M )   4 Mm  0
2

m  M sin 2
( ka / 2)
  2K (
4
)  4 K
2 2
0
mM mM

b  b 2  4ac
The 2 roots are: x1,2 
2a
K ( m  M ) m  M 4sin 2
(ka / 2) 1/ 2
 
2
K [( ) 
2
]
mM mM mM
 • So, the resulting quadratic equation for ω2 is:

• The two solutions for ω2 are:

• Since the chain contains N unit cells, there will be

2N normal modes of vibration, because there are
2N atoms and 2N equations of motion for masses
M & m.
 Solutions to the Normal Mode Eigenvalue Problem
ω(k) for the Diatomic Chain

w
A
B ω+ = “Optic” Modes
C

ω- = “Acoustic” Modes
–л/a 0 л/a 2л/a k

• There are two solutions for ω2 for each wavenumber k. That is, there are
2 branches to the “Phonon Dispersion Relation” for each k.
• From an analysis of the displacements, it can be shown that, at point A,
the two atoms are oscillating 180º out of phase, with their center of
mass at rest. Also, at point B, the lighter mass m is oscillating & M is at
rest, while at point C, M is oscillating & m is at rest.
Diatomic Chain Model: Kittel’s Notation!
The solution is:
K K

Optic Modes Near the BZ Center (qa << 1)

(Optic Branch)
The Optic Mode becomes:
(ω+)2  2K(M1 + M2)/(M1M2)
Gap or ω+  constant
The Acoustic Mode becomes:
(ω-)2  (½) Kq2/(M1 + M2)
qa or ω-  vsq

Acoustic Modes vs  sound velocity in the crystal.

(Acoustic Branch) Just like an acoustic wave in air!
 The Diatomic Chain Solution:
K K
( = 2a)
Optic Modes Near the BZ edge [q =  (π/a)]
(Optic Branch) (Assuming M1 > M2)
The Optic Mode becomes:
(ω+)2  2K/M2
Gap The Acoustic Mode becomes:
(ω-)2  2K/M1
So, at the BZ edge, the vibrations of
wavelength  = 2a for the 2 modes
qa behave as if there were 2 uncoupled
masses M1 & M2, vibrating
Acoustic Modes independently with identical springs
(Acoustic Branch)
of constant K.
• Again briefly examine limiting solutions at points 0, A, B & C. In the long
wavelength region near k = 0 (ka«1), sin(ka/2) ≈ ½ka.
w
A
B
C

–л/a 0 л/a 2л/a k

A Taylor’s series expansion, using for, small x:

K (m  M ) m  M 2 4sin 2 (ka / 2) 1/ 2
1,2 2  K [( )  ]
mM mM mM
 wA The root with the minus sign gives the
B
C minimum value of the acoustic branch:

K (m  M ) m  M 2 4sin 2 (ka / 2) 1/ 2
1,2 2  K [( )  ]
–л/a 0 л/a mM
2л/a k mM mM

The root with the positive sign gives the

maximum value of the optic branch:

Substituting these values of ω into the expression for the relative amplitude
α and using cos(ka/2) ≈1 for ka«1gives the corresponding value of α:

OR
  2
Substituting min ac into the expression for the relative amplitude α:
K(k 2 a 2 ) 2K   2 M  1
min
2
 
ac
2(m  M) 2 K cos(ka / 2)

This solution corresponds to long-wavelength vibrations near the

center of the BZ at k = 0. In that region, M & m oscillate with
same amplitude & phase. Also in that region ω = vsk, where vs is the
velocity of sound & has the form:
w 1/ 2
Optic A w  K 
B
vs   a  
C
k  2( m  M ) 
Acoustic

k
–π/ a 0 π/a 2π/a
  2
Similarly, substituting max op
into the relative amplitude gives:

2K(m  M) 2K   2 M M
 2
   
max op
mM 2 K cos(ka / 2) m

This solution corresponds to point A in

the figure. This value of α shows that,
w in that mode, the two atoms are
Optic A oscillating 180º out of phase with their
B
C center of mass at rest.

Acoustic

k
–π/a 0 π/a 2π/a
 w
A
• The other limiting solutions for B
C
ω2 are for ka = π. In this case
sin(ka/2) =1, so
1/ 2
K (m  M )  M  m 2
4 
  k
 
2
max ac K   –л/a 0 л/a 2л/a
Mm  Mm  Mm 
K (m  M ) K ( M  m) 2K 2K
  2
max ac  OR  2
min op 
Mm M m
(B)
(C)

• At point C in the plot, which is the maximum acoustic branch

point, M oscillates & m is at rest.
• By contrast, at point B, which is the minimum optic branch
point, m oscillates & M is at rest.
 Eigenmodes of chain at q = 0
Optical Mode:
These atoms, if
oppositely
charged, would
form an oscillating Center of the unit cell is not moving!
dipole which
would couple to
optical fields with <
aa  2f 2f 
 M 
2 f (M1  M 2 )  1 M 1M 2 
 ( q  0)  , D( q  0) 
M 1M 2  2f 2f 
 
 M 1M 2 M2 
2f 2 fM 1M 2 2f   u1 

 M (M  M )  
 1 1 2 M 1 M 2    0  u   M2 u , sn1 M
 2
 2f 2f 2 fM 1M 2   
1
M1
2
sn 2 M1
    
 M 1M 2 M 2 ( M 1  M )
2   u2 
Normal modes of chain in 2D space
• Constant force model (analog of TBH) : bond stretching and bond bending

0(  )  0

1(  )  

0(  )   r  

1(  )   r

1
    r     (s j  s i )  rˆij     s j  s i 
 2 2

2 ij  
1 
 (q) 
2
 r      r2  2  2 r cos(q  a) 
M  
 Quantum Mechanical Simple Harmonic Oscillator
• Quantum mechanical results for a simple harmonic oscillator
with classical frequency ω: The energy is quantized
 1
 nn   n 
E  n = 0,1,2,3,..
 2
• Energy levels are E
equally spaced!




Often, we consider En as being constructed by adding n excitation
quanta of energy  to the ground state.
1
E00   Ground state energy of the
2 oscillator.
If the system makes a transition from a lower energy level to a higher
energy level, it is always true that the change in energy is an integer
multiple of 

Phonon absorption or ΔE = (n – n΄) 

emission n & n ΄ = integers
In complicated processes, such as phonons interacting with
electrons or photons, it is known that phonons are not conserved.
That is, they can be created and destroyed during such
interactions.
Counting

This enumeration follows from counting the number of

degrees of freedom of the atoms. For p atoms in N
primitive cells, there are pN atoms. Each atom has 3
degrees of freedom, one for each of the 3 directions x,
y, and z. This gives 3Np degrees of freedom for the
crystal.
 Three Dimensions

i ( q  r t )
un  ue

Al Ge
Phonon Momentum

A phonon with a wavevector q will interact with particles, like

neutrons, photons, electrons, as if it had a momentum (the
crystal momentum)  
p  q
• Be careful! Phonons do not carry momentum like photons do. They can
interact with particles as if they have a momentum. For example, a
neutron can hit a crystal and start a wave by transferring momentum to
the lattice.
• However, this momentum is transferred to the lattice as a whole. The
atoms themselves are not being translated permanently from their
equilibrium positions.
• The only exception occurs when q = 0, where the whole lattice
translates. This, of course, does carry momentum.
 Phonon Momentum
For example, in a hydrogen
molecule the internuclear H2 electron
vibrational coordinate
r1 r2 is a relative
coordinate and doesn’t r R r
have linear momentum.

The center of mass

R
coordinate ½(r1 r2 ) Proton B
Proton A
corresponds to the uniform
mode q = 0 and can have r1 r2
linear momentum.

O
 Phonon Momentum
 
p  q
Earlier, we saw that the elastic scattering of x-rays from the
lattice is governed by the rule:   
k  k  G
If the photon scattering is inelastic, with a creation of a
If the photon is absorbed, then
phonon of wavevector q, then
   
kk 
 q kkGGq
Phonon Scattering (Normal Process)
q1

q3 = q1 + q2

q2

q3 = q1 + q2 or q3 = q1 + q2 + G
 Measuring Phonons

   
k  q  k  G
reciprocal lattice vector
scattered neutron

phonon wavevector
(+ for phonon created, incident neutron
 for phonon absorbed)

Stokes or anti-Stokes Process

Measuring Phonons

q
Measuring Phonons
 Measuring Phonons

Other Techniques
• Inelastic X-ray Spectroscopy
• Raman Spectroscopy (IR, near IR, and visible light)
• Microwave Ultrasonics