Chapter 5 : Thermal Properties

Einstein and Debye Models of Heat Capacity

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Lattice vibrations : Understanding various thermal properties

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• Quantized normal modes of vibration : PHONONS

• PHONONS : Quantum mechanical “particles”

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 Comparison of Phonons & Photons

PHONONS PHOTONS

• Quantized normal modes of • Quantized normal modes of

lattice vibrations. electromagnetic waves.
• Energies & momenta of • Energies & momenta of
phonons are quantized photons are quantized

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Quantum Mechanical Description :

• Simple harmonic oscillator with classical frequency ω:

 1
 n   n   n = 0,1,2,3,..
 2

E ħω

Energy ħω
levels are
ħω
equally spaced!
ħω

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 1 Oscillator Ground State
E00 =  (or “zero point”) Energy
2

System : Transition from a lower energy level to a higher energy level

(change in energy is an integer of  )

Phonon Absorption ΔE = (n - n΄) 

or Emission n & n΄ = integers

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 Thermal Energy & Lattice Vibrations

Atoms in a crystal vibrate about their equilibrium positions :

Produces vibrational waves

Amplitude of vibrational motion :

Increases as the temperature increases.

Energy associated with these vibrations : Thermal Energy

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• Thermal energy : Fundamental Role
(thermodynamic properties & others!)

Examples
Heat Capacity, Entropy, Helmholtz Free Energy, Equation of State

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Specific Heat or Heat Capacity

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Definition :
Amount of heat energy that must be supplied to a mole of solid to
raise its temperature by one degree.

• Increase in the vibration of atoms about their mean position

• Increase in the kinetic energy of free electrons

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Vibrational Specific Heat of Solids

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 Classical approach
Dulong - Petit law

 Quantum approach

1. Einstein's model
2. Debye's model

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 Historical Background

• In 1819 :
Molar heat capacity for solids is approximately

CV  3R

Dulong - Petit Law

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• Dulong-Petit “Law” :
Classical Maxwell-Boltzmann statistical physics

Specifically : Equipartition Theorem can be used.

Thermal average energy per degree of freedom is (½)kT

Atom : 6 degrees of freedom

1 
E  N A 6  kT   3RT R = NA k
2 

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 Heat Capacity at Constant Volume

1 
E  N A 6  kT   3RT
2 
3R
E  Cv
CV  
T V

T, K
CV  3R

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 Einstein Model of a Vibrating Solid

• Crystalline solid (N atoms) : Array of atomic oscillators

• Each atom vibrates in 3-dimensions (3N independent oscillators)
• Quantized Energy of a Single Oscillator

Number of oscillators (Nn ) of each energy state : Boltzmann function

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Average vibrational energy of an oscillator :

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Now, some straightforward math simplification!
Putting in the explicit form gives:

 1   1 
_  
n 0 
n 
2
  exp


 

n 
2
  / k T
B 

 
  1 

n 0
exp 
 
 
n 
2
  / k T
B 


1 
z   exp[(n  ) ]
n 0 2 k BT
 / 2 k BT  / 2 k BT  / 2 k BT
z  e  e 3  e 5  .....
x    / kBT  / 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

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The equation for ε can be rewritten :
_
1 z 
  k BT 2  k BT 2 (ln z )
z T T
  / 2 k BT
_
  e 
  k BT 2
ln  
T  1  e   / kBT 
 
 
_
  k BT 2 ln e   / 2 k BT
 ln 1  e   / k BT

T  
      
 
_
  / k BT
  k BT 2      ln 1  e
 T  2 k B T   T 
  k B   / k BT 
_  2k  k 2T 2 e  1  e   / k BT
  k BT  B2 2  B   / k T  
2

 4 k BT 1  e B
 2 1  e  / k BT

 
_
1 
Finally, the result is :    / k BT
2 e 1
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_
1 
    / k BT
2 e 1

Mean Phonon Energy

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 Einstein Heat Capacity CV

 kB 

 

kBT
e
 k BT 
_
1 d
2

   Cv  
e 
 / k BT
1  2
2 e dT kBT
1

 Cv  kB    2

2 kBT
  e
2
e T

 
Cv  k B   Let  
   kBT   2
T   2
e T
1 kB
e kBT
1

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Three independent harmonic oscillators : Whole solid
(3NCv)

 
2 k BT
e
 kB 3NkB  3R
e 
Cv
 B 
2  2
k T k BT
1

High Temperature Range :

3R

Cv

T, K
Cv = 3R (Classical Dulong - Petit law)

Specific heat of a given number of atoms of any solid :

Independent of temperature & is the same for all materials!

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Low Temperature Range :

 
2 k BT
e
 kB
e 
Cv
 B 
2  2
k T k BT
1

3R

Cv

T, K

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 Einstein Model for Lattice Vibrations in a Solid
Cv vs T for Diamond

Points : Experiment

Curve :
Einstein Model Prediction

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 Debye Model

Source of Error : Lies in the assumption (Vibrate independently at constant frequency)

Debye : Solid as a continuously vibrating medium

(Spectrum of frequencies instead of a single frequency)

Frequency distribution is known : Determine the TE and Cv

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 
1 
Lattice vibration energy E  (    / kBT )g ( )d
0
2 e 1

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• Each particular energy level can be associated with more than one
different state (or wavefunction ) : Degenerate energy level

• Density of states  ( ) :
Number of discrete states per unit energy interval, and so that the
number of states between  and   d  will be  ( )d  .

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 Debye Model

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

Number of modes with frequencies lie between  &  + d

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

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 Debye cut-off frequency D
Maximum frequency limiting the spectrum of Normal Modes
3N lattice vibration modes in a crystal having N atoms

Function, g() : Satisfy the normalization condition

D


0
g ( )d   3N

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

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

g ( ) /  2
9N
g ( )  2
D3
 
1 
Lattice vibration energy E   (    / kBT )g ( )d
0
2 e 1

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

D  

D
9 9N  3d
and, E  N D  3
8 D e
0
/ k BT
1

First term : Estimate of the zero point energy

 dE
Heat capacity is C
dT

D D
9 9N  3d dE 9 N 4
2
e  / k BT
E  N D  3 e CD   3 kT d
D 1 dT D e 
/ k BT 2 2
 / k BT
8 0 0 B 1

Let’s convert this complicated integral : Changing variables

 d k T
x  B
k BT dx 
 D
xD 
k BT

D
Define the Debye temperature D 
kB
Debye prediction for lattice specific heat

D / T
dE 9 N kBT  k BT   2 
4
x 4e x
CD      2   dx
dT D3    k BT  e  1
x 2
0

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

x is always small x2 x3
e  1 x 
x
 
 2! 3!
x
k BT
x 4e x x 4 (1  x)
x 4 (1  x)
   x 2

 e  1 1  x 1
2 2 2
x x

3  /T
 T  D

T   D  CD  9 NkB  
 D 
 0
x 2 dx  3Nk B
Low temperature region : T   D

3  /T
 T  D
x 4e x
T <  D  CD  9 NkB 
T<   dx 4 4 /15
 e  1
2
 D 0
x

3
12 NkB  T 
4
CD   
5 
 D

3
Debye T law
 Debye Model of Heat Capacity of Solids

Debye formula gives quite a good representation of the heat capacity of most solids