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
V2 1 V2 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
V2 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
