abeer alshammari 1

Energy Of Harmonic Oscillator

Obtained by in a classical way of considering the normal modes that

we have found are independent and harmonic.

 1
 n   n  
 2 • Make a transition to Q.M.

Energy, E
• Represents equally spaced
energy levels

 Energy levels of atoms


vibrating at a single
frequency ω


It is possible to consider  n as constructed by adding n excitation
quanta each of energy  to the ground state.
1
0  
2
A transition from a lower energy level to a higher energy level.

 1  1
   n2     n1  
 2  2

   n2  n1      
unity

absorption of phonon
• The converse transition results an emission of phonon with an energy  .
• Phonons are quanta of lattice vibrations with an angular frequency of  .
• Phonons are not localized particles.
• Its momentum is exact, but position can not be determined because of the uncertainity princible.
• However, a slightly localized wavepacket can be considered by combining modes of slightly
different  and  .

•Phonons are not conserved

•They can be created and destroyed during collisions .
 Thermal Energy And Lattice Vibrations

•Atoms vibrate about their equilibrium position.

•They produce vibrational waves.
•This motion is increased as the temperature is
raised.

In a solid, the energy associated with this vibration and perhaps also with
the rotation of atoms and molecules is called as thermal energy.

Note: In a gas, the translational motion of atoms and molecules

contribute to this energy.
abeer alshammari 5
 Therefore, the concept of thermal energy is fundamental to an understanding many
of the basic properties of solids. We would like to know:
• What is the value of this thermal energy?
• How much is available to scatter a conduction electron in a metal; since this
scattering gives rise to electrical resistance.
• The energy can be used to activate a crystallographic or a magnetic transition.
• How the vibrational energy changes with temperature since this gives a
measure of the heat energy which is necessary to raise the temperature of the
material.
• Recall that the specific heat or heat capacity is the thermal energy which is
required to raise the temperature of unit mass or 1gmole by one Kelvin.

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 Heat capacity from Lattice vibrations
The energy given to lattice vibrations is the dominant contribution to the heat
capacity in most solids. In non-magnetic insulators, it is the only contribution.
Other contributions;
• In metals from the conduction electrons.
• In magnetic materials from magneting ordering.
Atomic vibrations leads to band of normal mode frequencies from zero up to some
maximum value. Calculation of the lattice energy and heat capacity of a solid
therefore falls into two parts:
i) the evaluation of the contribution of a single mode, and
ii) the summation over the frequency distribution of the modes.
 Heat Capacity
You may remember from your study of
thermal physics that
the specific heat is the amount of energy per
unit mass required to raise the temperature
by one degree Celsius.
Q = mcT

Thermodynamic models give us this

definition:

 U 
CV   
 T V
Cv = yT+T3
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electrons phonons
 Heat Capacity
Equipartition Theorem (Classical model): The mean energy is
The internal energy of a system of N particles is spread equally over all
degrees of freedom,
hence the terminology –
3 Nk BT equipartition.

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,
Monatomic particles have only 3 translational degrees of freedom. They possess
no rotational or vibrational degrees of freedom.

  3Nk BT  3RT
where N is avagadro’s number, kB is boltzmann constant and R is the gas
constant. the differentiation wrt temperature gives;
d
Cv  Cv  3R  3  6.02 1023 (atoms / mole) 1.38 1023 ( J / K )
dT 9
J Cal
abeer alshammari Cv  24.9 ;1J  0.2388Cal  Cv 6
( K  mole) ( K  mole)
 • 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
In all of these materials
cal (Pb,Al, Si,and Diamond)
6
Kmol specific heat approaches
constant value asymptotically
at high T’s. But at low T’s, the
specific heat decreases
T towards zero which is in a
 complete contradiction with
Cv  3R the above classical result.
kB
 We Need To Use Quantum Statistics To Describe This Properly.

• Bosons And Fermions

• Bosons: Particles That Can Be In The Same Energy State (E.G. Photons, Phonons)
• Fermions: Particles That Cannot Be In The Same Energy Level (E.G. Electrons)

Phonons PHOTONS
• Quanta Of Lattice Vibrations • Quanta of electromagnetic radiation
• Energies of Photons are quantized as well
• Energies Of Phonons Are Quantized

h s hc
E phonon  E photon 
 
~a0=10-10m ~10-6m
h
p phonon  p photon 
h
 
Planck Distribution
 Planck Distribution

number of phonons in
energy level n

total number of phonons

all possible energy levels 0, 1, 2, etc.

 Planck Distribution

 n  n   nhf

Fraction of Nn e  n / kT e  n  / kT small as n gets large

Phonons  
 
 
at energy n
N e e
  n / kT  n  / kT a constant
n
0 0 0
 Planck Distribution
Average occupied
energy level


  
1 1 1

nn00
x n

1  x
 e 
n 0
n

1  e
 e
n 0
 n  / k BT

1  e   / k BT



   nn   1  x
 nx  x 
nnn
 xx  x   
n
n 0
n 00 x 
x  n 0 
n  0  x  1  x  1  x  2
 Energy And Heat Capacity Of A
Harmonic Oscillator, Einstein Model
_
   Pn n
n
Avarage energy of a harmonic
oscillator and hence of a lattice
mode of angular frequency at
temperature T Energy of oscillator

 1
The probability of the oscillator being in this n   n   
level as given by the Boltzman factor  2
exp( n / kBT )
 
1   1 
_   n    exp 
  n    / k T
B 
   Pn n       (*)
_
2 2
  n 0 
  1 

n
exp 
  n    / k T
B 
n 0   2  

1 
z   exp[(n  ) ]
n 0 2 k BT
 / 2 k BT  / 2 k BT  / 2 k BT
z  e  e 3  e 5  .....
 / 2 k BT  / k BT  / k BT
z  e (1  e   e 2  .....
 / 2 k BT  / k BT 1
z  e (1  e  )

According to the Binomial expansion for x«1 where x    / k BT

Eqn (*) can be written
_
1 z 2 
  k BT 2
 k BT (ln z )
z T T
_
2   e   / 2 k BT 
  k BT ln  
T  1  e   / kBT 
    / 2 k BT
 
_
  k BT 2 ln e  ln 1  e   / k BT

T  
      
ln 1  e 
_
  k BT   
2

  / k BT  x'
  (ln x) 
 
T 2 k B 
T T  x x
  k B   / k BT 
_  2k  k 2T 2 e  1 e  / k BT
  k BT 2  B2 2  B   / k T  
 4 k BT 1  e B   2 1  e   / k BT

 

_
1 
    / k BT
2 e 1
 _
1 
    / k BT
2 e 1
This is the mean energy of phonons.The first term in the above
equation is the zero-point energy. As we have mentioned before even
at 0ºK atoms vibrate in the crystal and have zero-point energy. This is
the minimum energy of the system.
The avarage number of phonons is given by Bose-Einstein
distribution as
_
(number of phonons) x (energy of phonon)=(second term in  )
1
n( )  

e k BT
1
The second term in the mean energy is the contribution of
phonons to the energy.
  k BT Mean energy of a
harmonic oscillator
as a function of T
1

2
T

low temperature limit

ℏ𝜔 ≫ 𝑘𝐵 𝑇

1_
 Since exponential term
      gets bigger
2 e kBT  1
_
1
   Zero point energy
2
  k BT Mean energy of a
harmonic oscillator as
a function of T
2
x
1
 e x  1  x   ..........
2 2!
T 

e kBT
 1
high temperature limit k BT
ℏ𝜔 ≪ 𝑘𝐵 𝑇 _
1 
   
2 
•  is independent of frequency of 1 1
oscillation. k BT
_
1
•This is the classical limit because the     k BT
energy steps are now small compared with 2
the energy of the harmonic oscillator.
•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 energy of phonons of

_
1 
     
2 e kBT  1
 kB 

  e k BT


 k BT   
2 2
d
k BT
e
Cv   Cv  k B
e   B 
 
 2 2  2
dT k T
k BT
1 e k BT
1


  
2
eT
Let  Cv  k B   

 T  e T 1

2
θ is Einestein Temperature k
 Einstein Model
How did Einstein do?

T 
 Einstein Model
How did Einstein do?

T 0K
 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 a heat capacity 3N times

 
2
e T

Cv  k B  
T 
e 
 2
T
1

• 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

3Nk B  3R
dulong-petit law where R is universal gas constant.
 The Discrepancy Of Einstein Model
• 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.(It is
exponential relation)

• Taking into account the actual distribution

of vibration frequencies in a solid this
discrepancy can be accounted using one
dimensional model of monoatomic lattice

The Einstein model failed to identically match the

behavior of real solids, but it showed the way.

In real solids, the lattice can vibrate at more than

one frequency at a time.
Dulong-Petit model (1819) • Einstein model (1907) •

• Atoms on lattice vibrate • Atoms on lattice vibrate

independently of each other • independently of each other •

• Completely classical • • Quantum mechanical (vibrations

are quantised) •
• Heat capacity independent of • Heat Capacity depends on
temperature (3NkB ) • Temperature

• Poor agreement with • Agreement with experiment good

experiment, except at high at very high (~3NkB ) and very low
temperatures (~0) temperatures, but not in
between
abeer alshammari 27
Debye model
Basic idea similar to Einstein model, with one key difference:

Einstein: Energy of system = Phonon Energy x Average number of phonons

Debye: Energy of system = Phonon Energy x Average number of phonons x number of modes

The number and

type of modes are
the key difference
Einstein: number of modes = number of atoms

Debye: each mode has its own k value (and hence frequency)
abeer alshammari 28
 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 𝐷(ε) is the number of discrete states per unit energy
interval, and so that the number of states between  and   d  will be
. 𝐷 𝜀 𝑑𝜀
 There are two sets of waves for solution;
• Running waves
• Standing waves
Running (Travelling) waves:
k
4 2 0 2 4 6
 
L L L L 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  pk  p Length of
p k Na L the 1D
chain

These allowed wavenumbers are uniformly distibuted in k at a

density of 𝐷𝑅 (𝑘) between k and k+dk.
𝑳
𝑫𝑹 𝒌 𝒅𝒌 = 𝒅𝒌
𝟐𝝅
running waves
 Standing waves: 5 4 3
L L L
6
k L 2
0  2 3 L
L L L 7 0 
L 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 for  for
k p k p
L running waves L standing waves
 These allowed k’s are uniformly distributed between k and k+dk
at a density of 𝐷𝑠 (𝑘)

𝑳
𝑫𝒔 𝒌 𝒅𝒌 = 𝒅𝒌 DOS of standing wave
𝝅
𝑳
𝑫𝑹 𝒌 𝒅𝒌 = 𝒅𝒌 DOS of running wave
𝟐𝝅

•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 Ds(k) and DR(k).

dR modes with frequency from  to +d corresponds

dn modes with wavenumber from k to k+dk

 𝑑𝑛 = 𝐷𝑅 𝑘 𝑑𝑘 = 𝑔 ;𝜔 𝑑𝜔 𝑑𝑛 = 𝐷𝑠 𝑘 𝑑𝑘 = 𝑔 𝜔 𝑑𝜔

Choose standing waves to obtain g ( )

𝑑𝑘
𝑔(𝜔) = 𝐷𝑠 𝑘
𝑑𝜔

Let’s remember dispertion relation for 1D monoatomic lattice

4K ka
2  sin 2 2
K
sin
ka
m 2 m 2

d 2a K ka
 cos
dk 2 m 2
1
K ka 𝑔(𝜔) = 𝐷𝑠 𝑘
a cos a
K
cos
ka
m 2 m 2
1 m 1
𝑔(𝜔) = 𝐷𝑠 𝑘
a K  ka 
cos  
 2 
 1 m 1
𝑔(𝜔) = 𝐷𝑠 𝑘
a K cos  ka / 2 

 ka   ka 
sin x  cos x  1  cos x  1  sin x
2 2 2 cos    1  sin 2  
 2   2 

1 m 1 4 Multibly and divide

𝑔(𝜔) = 𝐷𝑠 𝑘
a K  ka  4
1  sin 2  
 2 

1 2
𝑔(𝜔) = 𝐷𝑠 𝑘 Let’s remember:
a 4K 4K  ka 
 sin 2   𝐿
m m  2  𝐷𝑠 𝑘 𝑑𝑘 = 𝑑𝑘
𝜋
L 2 1 L  Na
g ( ) 
 a max
2
2 4K 2  ka 
 
2
sin  
m  2 
g ( )   max 
2 N  2   2 1/ 2
  2

4K
max
True density of states
m
 g ( )
g ( ) 
2N

 2
max  
2 1/ 2

N m
True density of states by
 K means of above equation

K K
max 2 
m 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

1  
      / kT   g   d
0
2 e 1 

Mean energy of a harmonic

2N

 2
max   for 1D
2 1/ 2

oscillator

It should be better to find 3D DOS in order to compare the

results with experiment.
 Vk 2
• 𝐷  k   is a new density of states in 3D.This eqn can be obtained by
2 2
using running waves as well.

• (frequency) space can be related to k-space:

dk
g   d  𝐷  k  dk g    
𝐷 k 
d

Let’s find C at low and high temperature by means of

using the expression of g   .

 High And Low Temperature Limits

Each of the 3N lattice d

  3NkBT modes of a crystal C C  3NkB
containing N atoms dT

• this result is true only if


T≫ 
kB

• At low T’s only lattice modes having low frequencies can be

excited from their ground states;

Low frequency long 

sound waves

  vs k vs 
 k k
0
a
  1 k
dk 1 Vk 2 dk
vs      and g   
k  vs d vs 2 2 d 

 2 
V 2 
g     vs  1
at low T’s
2 2 vs

vs depends on the direction and there are two transverse,

one longitudinal acoustic branch:
V2 1 V2  1 2 
g     g    2  3
 3
2 vs
2 3
2  vL vT 

Velocities of sound in
longitudinal and
transverse direction
 
1  
      / kT   g   d Zero point energy=  z
0
2 e 1 

1   V  1 2 
2
      / kT   2  3  3  d
0
2 e  1  2  vL vT 
 V  1 2  

3  
   z  2  3  3      / kT d  x
 2  vL vT    0  e  1  kBT
  k BT
 k BT  3
3  x
    x
 3
  k BT k BT
0 e  / kT  1 d   0 e x  1 dx d  dx

 k BT 
4 
 3
x3
e 
0
/ kT
1
d  3 0 e x  1dx
V  1 2   k BT   4
4
 4 15
at low temperatures
  z  2  3  3 
d 1 2   kBT 
3
2  vL vT  3
15 2
Cv   V  kB  3  3
2
 
d V  2  1 2  4 3
Cv   3  3
 3  k B 4T dT 15  vL vT  
dT 30  vL vT 
 How Good İs The Debye
Approximation At Low T?
d  1 2   k BT 
3
2
Cv   V  kB  3  3  
2

dT 15  L
v vT   

The lattice heat capacity of solids thus

varies as T 3 at low temperatures; this is
referred to as the Debye T3 law.
Figure illustrates the excellent aggrement
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 İnterpolation Scheme

the calculation of g ( ) 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. ın a one dimensional crystal this is
equivalent to taking g ( ) as given by the broken line of density of
states figure rather than full curve. debye’s approximation gives the
correct answer in either the high and low temperature limits, and 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 Debye
approximation approximation
to the to the
dispersion dispersion
  vk
 Debye Cut-off Frequency D
2. ensure the correct number of modes by imposing a cut-off
frequency D , 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 D so that
D

 g ( )d   3 N
0 
V 1 2
2 V 1 2 D 2
2 2 vL3 vT3 0
g ( )  ( 3  3) (  )  d  3N
2 vL vT
2

V 1 2 3N 9N
V 1

2
)D3  3 N (  )  3 
6 2
( 3
vL vT 3 2 2 vL3 vT3 D3 D3

9N
g ( )  2 g ( ) /  2
D3
the lattice vibration energy of


1 
E   (    / kBT )g ( )d
becomes 0
2 e 1
D
9N 1  9N D  3 D
3 
E 3 0 2 e  / kBT  1
      d   d 
2
( ) d  / k BT
D D3  0 2 0
e  1 

D
9 9N  3d
and
E  N D  3
8 D e
0
/ k BT
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.
 dE
The heat capacity is C
dT
D
D
 d3
dE 9 N  4 e  / k BT
2


9 9N
E  N D  3  CD   3 d
8 D 0
e  / k BT  1 dT D 0
kBT  e  / kBT  1
2 2

Let’s convert this complicated integral into an expression for

the specific heat changing variables to x

 d kT 
kT
x  x
k BT dx

and define the Debye temperature D

D
D 
kB
The Debye prediction for lattice specific heat

D / T
dE 9 N kBT  kBT   
4 2
x 4e x
CD   3    2   dx
dT D    kBT   e 1
x 2
0

3  /T
 T  D
x 4e x
CD  9 Nk B    dx
   1
2
 D 0 e x

D
where D 
kB
How does CD limit at high and low temperatures?

High temperature • 𝑇 ≫ Θ𝐷
x2 x3
X is always small e  1 x 
x
 
2! 3!

x 4e x x 4 (1  x) x 4 (1  x)
   x 2

   
2 2
 
2
e x
 1 1 x 1 x

3  /T
 T  D

T  D  CD  9 Nk B 

 D
 0
x 2 dx  3Nk B
 How does CD limit at high and low temperatures?

Low temperature • 𝑇 ≪ Θ𝐷
9 9𝑁ℏ 𝜋 4 𝑘𝑇 4
D
9 9N  3d 𝐸 = 𝑁ℏ𝜔𝐷 + 3 ( )

8 𝜔𝐷 15 ℏ
E  N D  3
8 D 0
e  / k BT  1
9𝑁ℏ 𝜋 4 𝑘 4 3
𝜔𝐷 𝐶𝐷 = 0 + 3 ( ) 4𝑇
9 9𝑁ℏ 𝑘𝐵 𝑇 3 𝑥 3 𝑘𝑇 𝑑𝑥
𝐸 = 𝑁ℏ𝜔𝐷 + 3 ( ) 𝑥 𝜔𝐷 15 ℏ
8 𝜔𝐷 0 ℏ 𝑒 −1 ℏ D
D 
For low temperature the upper limit of the integral is kB
infinite; the integral is then a known integral of

x is very large We obtain the Debye T 3 law in the form

∞
9 9𝑁ℏ 𝑘𝑇 4 𝑥3 3
𝐸 = 𝑁ℏ𝜔𝐷 + ( ) 𝑑𝑥 12 Nk B 4  T 
8 𝜔𝐷 ℏ 𝑒𝑥 − 1 CD   
0
5 
 D
Lattice Heat Capacity Due To Debye İnterpolation Scheme

figure shows the heat capacity C

between the two limits of high and low 3Nk BT
t as predicted by the debye 1
interpolation formula.
3  /T
 T  D x 4e x
CD  9 Nk B    dx
 D  0  e  1
 x 2

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, 1
T / D
even though the actual phonon-density of states Lattice heat capacity of a solid as
curve may differ appreciably from the Debye predicted by the Debye interpolation
scheme
assumption.
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
for  D various solids is given in table. Debye energy D can be used to estimate
the maximum phonon energy in a solid.
Solid Ar Na Cs Fe Cu Pb C KCl
D ( K ) 93 158 38 457 343 105 2230 235
 Specific Heats of Lead, Silver, Aluminum and Diamond

abeer alshammari 54
 Anharmonic Effects
• Any real crystal resists compression to a smaller volume than its equilibrium value more
strongly than expansion due to a larger volume.
• This is due to the shape of the interatomic potential curve.
• This is a departure from hooke’s law, since harmonic application does not produce this
property.
• This is an anharmonic effect due to the higher order terms in potential which are ignored in
harmonic approximation.

• Thermal expansion is an example to the anharmonic effect.

• In harmonic approximation phonons do not interact with each other, in the absence of
boundaries, lattice defects and impurities (which also scatter the phonons), the thermal
conductivity is infinite.
• In anharmonic effect phonons collide with each other and these collisions limit thermal
conductivity which is due to the flow of phonons.
Rising temperature results
in the increase of the
average amplitude of
atomic vibrations. For an
anharmonic potential, this
corresponds to the increase
in the average value of
interatomic separation, i.e.
thermal expansion.

abeer alshammari 56
Thermal expansion is
related to the asymmetric
(anharmonic) shape of
interatomic potential. If
the interatomic potential is
symmetric (harmonic), the
average value of
interatomic separation
does not change, i.e. no
thermal expansion.

abeer alshammari 57
 Phonon-phonon Collisions

The coupling of normal modes by the unharmonic terms in the

interatomic forces can be pictured as collisions between the phonons
associated with the modes. A typical collision process of

phonon1 3 , k3
1 , k1
After collision another phonon is
produced

2 , k 2
phonon2 3  1  2 and k3  k1  k2
3  1  2 conservation of energy

k3  k1  k2 conservation of momentum
Phonons are represented by wavenumbers with
 
 k
a a
2
If k3 lies outside this range add a suitable multible of a
to bring
it back within the range of    k   . Then, k3  k1  k2 becomes
a a
n 2
This phonon is indistinguishable
k3   k1  k2
from a phonon with wavevector k3 a
where k1 , k2 , and k3 are all in the above range.
Longitudinal  3 3'  3
1 1 2
Transverse 2
k k
 0   0 
 
a a a a
n  0  Umklapp process
n  0  Normal process
(due to anharmonic effects)

 
Phonon3 has k ; Phonon3 has k and Phonon3=Phonon3’
a a
 Thermal Conduction By Phonons
• Thermal conductivity is the property of a material's ability to conduct heat.
• A flow of heat takes place from a hotter region to a cooler region
when there is a temperature gradient in a solid.
• The most important contribution to thermal conduction comes from
the flow of phonons in an electrically insulating solid.
• Transport property is an example of thermal conduction.
• Transport property is the process in which the flow of some quantity
occurs.
• Thermal conductivity is a transport coefficient and it describes the
flow.
• The thermal conductivity of a phonon gas in a solid will be
calculated by means of the elementary kinetic theory of the transport
coefficients of gases.
 Kinetic Theory

In the elementary kinetic theory of gases, the steady state flux of a property P
İn the z direction is 1 _ dP
flux  l 
3 dz
Angular average
Constant average speed for molecules
Mean free path
In the simplest case where P is the number density of particles the transport
_
coefficient obtained from above eqn. is the diffusion coefficient D  1 l  .
3
If P is the energy density E then the flux W is the heat flow per unit area so that
1 _ dE 1 _ dE dT
W  l  l
3 dz 3 dT dz
Now dE / dT is the specific heat C per unit volume, so that the thermal
conductivity;
1 _
K  l C Works well for a phonon gas
3
 Heat Conduction İn A Phonon And Real Gas
The Essential Differences Between The Processes Of Heat
Conduction İn A Phonon And Real Gas;

Phonon gas Real gas

•Speed is approximately constant. •No flow of particles

•Both the number density and energy •Average velocity and kinetic energy per
density is greater at the hot end. particle are greater at the hot end, but the
number density is greater at the cold end,
•Heat flow is primarily due to phonon
and the energy density is uniform due to the
flow with phonons being created at the
uniform pressure.
hot end and destroyed at the cold end
•Heat flow is solely by transfer of kinetic
energy from one particle to another in
collisions which is a minor effect in phonon
case.

hot cold hot cold

 Temperature Dependence Of Thermal Conductivity K

1 _
K  l C Approximately equal to
3 velocity of sound and so
Vanishes exponentially at
temperature independent.
low T’s and tends to classical
value k B at high T’s

•Temperature dependence of phonon mean free length is determined by phonon-phonon

collisions at low temperatures
•Since the heat flow is associated with a flow of phonons, the most effective collisions for
limiting the flow are those in which the phonon group velocity is reversed. It is the Umklapp
processes that have this property, and these are important in limiting the thermal conductivity
 Conduction At High Temperatures

• At temperatures much greater then the debye temperature  the heat capacity is given
D
by temperature-independent classical result of
C  3NkB
• The rate of collisions of two phonons  phonon density.

• If collisions involving larger number of phonons are important, however, then the
scattering rate will increase more rapidly than this with phonon density.

• At high temperatures the average phonon density is constant and

the total lattice energy  T; phonon number  T , so
scattering rate  T and mean free length  T
_
1

 T
Then the thermal conductivity of 1 .
K  l C 1
3
• Experimental results do tend towards this behaviour at high temperatures as
shown in figure (a).

10

10 0

0
1
10-1 T3
T
10-1

5 10 20 50 100 2 5 10 20 50 100
T (K ) T (K )

(a)Thermal conductivity of a quartz (b)Thermal conductivity of artificial

crystal sapphire rods of different diameters
 Conduction At İntermediate Temperatures

Referring figure a
At T<  D ; the conductivity rises more steeply with falling temperature, although the heat capacity is falling in this
region. Why?

This is due to the fact that umklapp processes which will only occur if there are phonons of sufficient energy to create a
phonon with k3   / a . so

Energy of phonon must be  the debye energy ( k D )

the energy of relevant phonons is thus not sharply defined but their number is expected to vary roughly as
e  D / bT when 𝑇 < 𝜃𝐷 ,
Where b is a number of order unity 2 or 3. Then l  eD / bT

This exponential factor dominates any low power of T in thermal conductivity,

Such as a factor of T 3 from the heat capacity.
 Conduction At Low Temperatures
l For phonon-phonon collisions becomes very long at low T’s and eventually exceeds the size of the solid,
because

Number of high energy phonons necessary for umklapp processes decay exponentially as

 D / bT
e
l İs then limited by collisions with the specimen surface, i.E.

l  Specimen diameter

T dependence of k comes from Cv which obeys T 3 law in this region

3
12 Nk B  T 
4
CD    Temperature dependence of C dominates.
5 
 D v
 Size Effect
• When the mean free path becomes comparable to the dimensions of the sample, transport
coefficient depends on the shape and size of the crystal. This is known as a size effect.

• If the specimen is not a perfect crystal and contains imperfections such as dislocations, grain
boundaries and impurities, then these will also scatter phonons. At the very lowest t’s the
dominant phonon wavelength becomes so long that these imperfections are not effective
scatterers, so;
The thermal conductivity has a T 3 dependence at these temperatures.

• The maximum conductivity between T 3 and  D / bT region is controlled by imperfections.

e
• For an impure or polycrystalline specimen the maximum can be broad and low [figure (a)],
whereas for a carefully prepared single crystal, as illustrated in figure(b) , the maximum is
quite sharp and conductivity reaches a very high value, of the order that of the metallic copper
in which the conductivity is predominantly due to conduction electrons.