Phonons

The Quantum Mechanics of Lattice Vibrations

What is a Phonon?
Weve 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
solids 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

PHOTONS

Quantized normal modes of lattice vibrations. The Quantized normal modes of electromagnetic waves.
The energies & momenta of photons are quantized
energies & momenta of phonons are quantized

h s
E phonon

h
p phonon

Phonon wavelength:
phonon a0 10-10 m

E photon
p photon

hc

Photon wavelength (visible):

photon 10-6 m

Quantum Mechanical Simple Harmonic Oscillator

Quantum mechanical results for a simple harmonic oscillator
with classical frequency : The energy is quantized

E
nn n

Energy levels are

equally spaced!

1

2

n = 0,1,2,3,..

Often, we consider En as being constructed by adding n excitation

quanta of energy to the ground state.
1
E
Ground state energy of the
00
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
emission

E = (n n)
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.

Thermal Energy & Lattice Vibrations

As weve been discussing in detail, 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 its

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.

Vibrational Specific Heat of Solids

cp Data at T = 298 K

Thermal Energy & Heat Capacity

Einstein Model
_

Pn n
Average energy of a harmonic
oscillator and hence of a lattice
mode of angular frequency at
temperature T

Energy of oscillator

1
n n h
2

The probability of the oscillator being in

this level as given by the Boltzman factor

exp( n / k BT )

Pn n
n

n h exp n h / k BT
_
2

n 0

exp n h / k BT

2
n0

1 h
z exp[(n )
]
2 k BT
n0

z e h / 2 kBT e 3h / 2 kBT e 5 h / 2 kBT .....

z e h / 2 kBT (1 e h / kBT e 2 h / kBT .....
z e h / 2 kBT (1 e h / kBT ) 1
According to the Binomial expansion for x1 where

x h / k BT

(*)

Eqn (*) can be written

1 z

k BT 2
(ln z )
z T
T
_
e h / 2 kBT
2
k BT
ln

T 1 e h / kBT
_

k BT 2

h / 2 k BT
h / k BT

ln
e

ln
1

k BT 2

k BT 2

k BT
2

h k B h / kBT
e
2 2
2k B h k B T

4k B2T 2
1 e h / kBT

1
h e h / kBT
h
2

1 e h / kBT

1
h
h h / kBT
2
e
1
_

Finally, the
result is

h / k BT

ln
1

2k BT
T

x'
(ln x)
x
x

1
h
h h / kBT
2
e
1
_

This is the Mean Phonon Energy. The first term in the above
equation is the zero-point energy. As mentioned before even at 0K
atoms vibrate in the crystal and have zero-point energy. This is the
minimum energy of the system.

The average number of phonons is given by the Bose-Einstein

distribution as
_
(number of phonons) x (energy of phonon) = (second term in )

n( )

1
e

k BT

The second term in the mean energy is the phonon contribution to the
thermal energy.

k BT

Mean energy of a
harmonic oscillator
as a function of T

2
T

Low Temperature Limit

k BT

2
e kBT 1
_

1

2
_

Since exponential term

gets bigger

Zero Point Energy

k BT

Mean energy of a
harmonic oscillator
as a function of T

x2
e 1 x ..........
2!
x

e
1
High Temperature Limit
k BT
_
1

h =
<< k BT

2
is independent of frequency of oscillation.
1
1
k BT
This is the classical limit because the energy
_
1
k BT
steps are now small compared with the energy
2
of the harmonic oscillator.

k BT

So that is the thermal energy of the

classical 1D harmonic oscillator.

kBT

Heat Capacity C
Heat capacity C can be found by differentiating the average phonon
energy

2
e kBT 1
_

d
Cv

dT

Let

h k B

k BT

h
kBT

k BT

Cv k B
2
k
T
B
2

Cv k B
T

e
e

k BT

e 1

k BT


Cv k B
T

e 1

where

h
k

Specific heat in this approximation

vanishes exponentially at low T and
tends to classical value at high
temperatures.

Cv

kB
h
Area =
2
h
kB

These features are common to all

quantum systems; the energy tends to
the zero-point-energy at low T and to
the classical value of Boltzmann
constant at high T.

Specific heat at constant volume depends on temperature as shown in

figure below. At high temperatures the value of Cv is close to 3R,
where R is the universal gas constant. Since R is approximately 2
cal/K-mole, at high temperatures Cv is app. 6 cal/K-mole.

3R
Cv
T,K

This range usually includes RT.

From the figure it is seen that Cv is
equal to 3R at high temperatures
regardless of the substance. This fact is
known as Dulong-Petit law. This law
states that specific heat of a given
number of atoms of any solid is
independent of temperature and is the
same for all materials!

Cv vs T for Diamond
Points:
Experiment
Curve:
Einstein Model
Prediction

Classical Theory of Heat Capacity of Solids

The solid is one in which each atom is bound to its side
by a harmonic force. When the solid is heated, the atoms
vibrate around their sites like a set of harmonic oscillators.
The average energy for a 1D oscillator is kT. Therefore, the
averaga energy per atom, regarded as a 3D oscillator, is 3kT,
and consequently the energy per mole is
= 3NkBT 3RT
where N is Avagadros number, kB is Boltzmann constant and R is the gas
constant. The differentiation wrt temperature gives;

d
Cv
dT
Cv 24.9

Cv 3R 3 6.02 1023 (atoms / mole) 1.38 1023 ( J / K )

J
Cal
;1J 0.2388Cal Cv ; 6
( K mole)
( K mole)

Einstein heat capacity of solids

The theory explained by Einstein is the first quantum theory of solids.
He made the simplifying assumption that all 3N vibrational modes of a
3D solid of N atoms had the same frequency, so that the whole solid had
2
a heat capacity 3N times
e

Cv k B

In this model, the atoms are treated as independent oscillators, but the energy
of the oscillators are taken quantum mechanically as
This refers to an isolated oscillator, but the atomic oscillators in a solid are not
isolated.They are continually exchanging their energy with their surrounding
atoms.
Even this crude model gave the correct limit at high temperatures, a heat
capacity of the Dulong-Petit law where R is universal gas constant.

3Nk B 3R

 At high temperatures, all crystalline solids have a specific heat of

6 cal/K per mole; they require 6 calories per mole to raise their
temperature 1 K.
This arrangement between observation and classical theory break
down if the temperature is not high.
Observations show that at room temperatures and below the
specific heat of crystalline solids is not a universal constant.
Cv
6

cal
Kmol

h
kB

T
Cv 3R

In each of these materials (Pb,Al,

Si,and Diamond) specific heat
approaches constant value
asymptotically at high T. But at
low Ts, the specific heat
decreases towards zero which is
in a complete contradiction with
the above classical result.

 Einstein model also gave correctly a specific heat

tending to zero at absolute zero, but the
temperature dependence near T= 0 did not agree
with experiment.
Taking into account the actual distribution of
vibration frequencies in a solid this discrepancy
can be accounted using one dimensional model of
monoatomic lattice

Thermal Energy & Heat Capacity

Debye Model

Density of States
According to Quantum Mechanics if a particle is constrained;
the energy of particle can only have special discrete energy values.
it cannot increase infinitely from one value to another.
it has to go up in steps.

 These steps can be so small depending on the system that

the energy can be considered as continuous.
This is the case of classical mechanics.
But on atomic scale the energy can only jump by a discrete
amount from one value to another.

Definite energy levels

Steps get small

Energy is continuous

 In some cases, each particular energy level can be

associated with more than one different state (or
wavefunction )
This energy level is said to be degenerate.

( )

The density of states

is the number of discrete
states per unit energy interval, and so that the number
of states between and d will be ( )d .

There are two sets of waves for solution;

Running waves
Standing waves
Running waves:

4
L

2
L

2
L

4
L

6
L

These allowed k wavenumbers corresponds to the running

waves; all positive and negative values of k are allowed. By
means of periodic boundary condition
an integer

Na 2
2
2
L Na p

k
pk
p
p
k
Na
L

Length of
the 1D chain

These allowed wavenumbers are uniformly distibuted in k at a

density of R k between k and k+dk.
running waves

L
R k dk
dk
2

Standing waves:
0

2
L

3
L

6
L

5
L

7
L

4
L

3
L

2
L

In some cases it is more suitable to use standing waves,i.e. chain

with fixed ends. Therefore we will have an integral number of half
wavelengths in the chain;
n
2
2 n
n
L ;k
k
k
2

2L
L
These are the allowed wavenumbers for standing waves; only
positive values are allowed.
2
k
p
L

for
running waves

k p
L

for
standing waves

These allowed ks are uniformly distributed between k and k+dk

at a density of S (k )
L
S (k )dk dk

L
R k dk
dk
2

DOS of standing wave

DOS of running wave

The density of standing wave states is twice that of the running waves.
However in the case of standing waves only positive values are
allowed
Then the total number of states for both running and standing waves
will be the same in a range dk of the magnitude k
The standing waves have the same dispersion relation as running
waves, and for a chain containing N atoms there are exactly N distinct
states with k values in the range 0 to / a .

The density of states per unit frequency range g():

The number of modes with frequencies and +d

will be g()d.
g() can be written in terms of S(k) and R(k).
dR

dn

modes with frequency from to +d corresponds

modes with wavenumber from k to k+dk

dn S (k )dk g ( )d

dn R (k )dk g ( )d ;

Choose standing waves to obtain

g ( )

g ( ) S (k )

dk
d

Lets remember dispertion relation for 1D monoatomic lattice

4K
2 ka

sin
m
2
2

d
2a

dk
2

K
ka
cos
m
2

K
ka
2
sin
m
2
g ( ) S (k )

1
K
ka
a
cos
m
2

1
g ( ) S ( k )
a

m
1
K cos ka / 2

sin x cos x 1 cos x 1 sin x

2

1
g ( ) S (k )
a

m
K

1
ka

1 sin 2

4
4

ka
2 ka
cos 1 sin
2
2

Multibly and divide

Lets remember:

g ( ) S (k )

1
a

2
4K 4K
2 ka

sin
m
m
2

1
L2
g ( )
2
a max
2
True density of states

L
S (k )dk dk

L Na
4K
2
2 ka

sin
m
2
4K
2
max
m

g ( )

2N 2
2 1/ 2
g ( )
max

m
K

True density of states by

means of above equation

max

K
2
m

constant density of states

K
True DOS(density of states) tends to infinity at max 2 ,
m
since the group velocity d / dk goes to zero at this value of .

Constant density of states can be obtained by ignoring the

dispersion of sound at wavelengths comparable to atomic spacing.

The energy of lattice vibrations will then be found by

integrating the energy of single oscillator over the distribution
of vibration frequencies. Thus

h
1
h h / kT g d
2
e
1
0

Mean energy of a harmonic

oscillator

2N 2
2 1/ 2
max for 1D

One can obtain same expression of g ( ) by means of using

running waves.
It should be better to find 3D DOS in order to compare the
results with experiment.

3D DOS
Lets do it first for 2D
Then for 3D.
Consider a crystal in the shape of 2D box with crystal lengths of L.

ky

kx

Standing wave pattern for a 2D

box

Configuration in k-space

Lets calculate the number of modes within a range of

wavevector k.
Standing waves are choosen but running waves will lead
same expressions.
Standing waves will be of the form
U U 0 sin k x x sin k y y
Assuming the boundary conditions of
Vibration amplitude should vanish at edges of
x 0; y 0; x L; y L
Choosing
p
q
kx
; ky
L
L

positive integer

ky

y
L
0

kx

Standing wave pattern for a

2D box

Configuration in k-space

The allowed k values lie on a square lattice of side

positive quadrant of k-space.

in
/the
L

These values will so be distributed uniformly with a density of

2
L
/

per unit area.

This result can be extended to 3D.

Octant of the crystal:

kx,ky,kz(all have positive values)
The number of standing waves;
L

V 3
L
3
s k d k d k 3 d k

1
4 k 2 dk
L /
8
V 1
3
s k d k 3 4 k 2 dk
8
2
Vk
s k d 3k 2 dk
2
ky
Vk 2
S k 2
2
3

kz
dk

kx

Vk 2 is a new density of states defined as the number of

k 2
2
states per unit magnitude of in 3D.This eqn can be obtained by
using running waves as well.
(frequency) space can be related to k-space:
dk
g k
g d k dk
d
Lets find C at low and high temperature by means of using the
expression of

.
g

High and Low Temperature Limits

3Nk BT

Each of the 3N lattice

modes of a crystal
containing N atoms

d
C
dT

C 3 Nk B

This result is true only ifT ?

kB
At low Ts only lattice modes having low frequencies can be
excited from their ground states;

long

Low frequency

sound waves
vs k
0

vs
k


k 1
dk 1
vs

k
vs
d vs
2
V 2
vs 1

g
2 2 vs

and

Vk 2 dk
g 2
2 d

at low T

depends on the direction and there are two transverse, one

vs
longitudinal
acoustic branch:
V2 1
V 2 1 2
g
g
3
2
3
2
3
2 vs
2 vL vT
Velocities of sound in longitudinal and transverse direction

h
1
h h / kT g d
2
e
1
0

Zero point energy = z

h
V 2 1 2
1
h h / kT 2 3 3 d
2
e
1
2 vL vT
0
V 1 2
z 2 3 3
2 vL vT

h
x
k BT

h 3
0 eh / kT 1 d

V 1 2 k T
z 2 3 3 B 3
2 vL vT
h

k BT
h
x3

3
h
k BT
h
4
d

dx
h / kT
x

1
e

1
h
15 0
0

k BT

h
0 eh / kT 1 d h3

k BT

x
h
k BT
d
dx
h

x3
0 e x 1dx
14 2 43
4 15

1 2 k BT
d
2
2
Cv
V k B 3 3

dT 15
v
v
h

L
T

at low temperatures

How good is the Debye approximation at low T?

1
d
2
2 k BT
2
Cv
V k B 3 3

dT 15
v
v
h

L
T

The lattice heat capacity of solids

thus varies as T 3at low
temperatures; this is referred to
as the Debye T 3 law. Figure
illustrates the excellent
agreement of this prediction with
experiment for a non-magnetic
insulator. The heat capacity
vanishes more slowly than the
exponential behaviour of a
single harmonic oscillator
because the vibration spectrum
extends down to zero frequency.

The Debye interpolation scheme

g (
The calculation of
is)a very heavy calculation for 3D, so it
must be calculated numerically.
Debye obtained a good approximation to the resulting heat capacity
by neglecting the dispersion of the acoustic waves, i.e. assuming

s k
for arbitrary wavenumber. In a one dimensional crystal this is
equivalent to taking
as given by the broken line of density of
states figure rather than full curve. Debyes approximation gives the
g (high
) and low temperature limits, and the
correct answer in either the
language associated with it is still widely used today.

The Debye approximation has two main steps:

1. Approximate the dispersion relation of any branch by a linear
extrapolation of the small k behaviour:
Einstein
approximation to
the dispersion

Debye
approximation
to the dispersion

vk

Debye cut-off frequency D

2. Ensure the correct number of modes by imposing a cut-off
D
frequency
,
above
which there are no modes. The cut-off
freqency is chosen to make the total number of lattice modes
correct. Since there are 3N lattice vibration modes in a
crystal having N atoms, we choose
so that D
D

V2 1 2
g ( )
( 3 3)
2
g ( )d 3 N
2 vL vT

V
1
2
(

)D3 3 N
2
3
3
6
vL vT

g ( )

9N 2

3
D

V 1 2 D 2
( ) d 3N
2 2 vL3 vT3 0

V
1
2
3N
9N
(

2 2 vL3 vT3
D3
D3

g ( ) / 2

The lattice vibration energy of

becomes

and,

9N
E 3
D

1
h
E ( h h / kBT )g ( )d
2
e
1
0

1
h
9N
2
0 ( 2 h eh / kBT 1) d D3

9
9N
E N hD 3
8
D

h 3
d
2

h 3
eh / kBT

h 3 d
e h / kBT 1

First term is the estimate of the zero point energy, and all T dependence
is in the second term. The heat capacity is obtained by differentiating
above eqn wrt temperature.

d
1

The heat capacity is

9
9N
E N hD 3
8
D

h d
e h / kBT 1
3

dE
dT

dE 9 N
CD 3
dT D

h2 4 eh / kBT
d
2
2
kBT eh / kBT 1

Lets convert this complicated integral into an expression for the

specific heat changing variables to
x

h
k BT

d
kT

dx
h

and define the Debye temperature

hD
kB

kT
x
h

The Debye prediction for lattice specific heat

4

dE 9 N k BT k BT h
CD
3

2
dT D h h k BT

T
CD 9 Nk B

where

3 /T
D

hD
kB

D / T

x 4e x

e 1
x

x 4e x

dx

dx

How does CD limit at high and low temperatures?

High temperature
x is always small

T ? D

x2
x3
e 1 x

2!
3!
x

x 4 (1 x )
2

x
2
2
2
x
x
1

e 1
x 4e x

x 4 (1 x)

T
T ? D CD 9 Nk B

3 /T
D

x 2 dx 3Nk B

How does CD limit at high and low temperatures?

Low temperature

T = D

For low temperature the upper limit of the integral is infinite; the
integral is then a known integral of
.
4 4 /15

T
T = D CD 9 Nk B

3 /T
D

x 4e x

dx

We obtain the Debye T 3 law in the form

CD

12 Nk B T

D
4

Lattice heat capacity due to Debye interpolation scheme

T
CD 9 Nk B

Figure shows the heat capacity D

between the two limits of high and

low T as predicted by the Debye
interpolation formula.

3 D / T

x 4e x

dx
C
3Nk B T

Because it is exact in both high and low T limits

the Debye formula gives quite a good
representation of the heat capacity of most
solids, even though the actual phonon-density
of states curve may differ appreciably from the
Debye assumption.

Lattice heat capacity of a solid as

predicted by the Debye interpolation
scheme

T / D

Debye frequency and Debye temperature scale with the velocity of sound in the solid.
So solids with low densities and large elastic moduli have high D . Values of Dfor
various solids is given in table. Debye energyhD
can be used to estimate the
maximum phonon energy in a solid.
Solid
D (K )

Ar

Na

Cs

Fe

Cu

Pb

KCl

93

158

38

457

343

105

2230

235