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 Avagadro’s number, kB is Boltzmann constant and
R is the gas constant. The differentiation w.r.t. temperature
gives;
d
Cv  Cv  3R  3  6.02  1023 (atoms / mole)  1.38  1023 ( J / K )
dT
J Cal
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 (Pb,Al,
cal Si,and Diamond) specific heat
6
Kmol approaches constant value
asymptotically at high T’s. But at
low T’s, the specific heat
decreases towards zero which is
T in a complete contradiction with
 the above classical result.
Cv  3R
kB
 Einstein heat capacity of solids
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
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.
• n 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.
 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 )
 h
  hf ( )  h
e kT
1
This is the mean energy of phonons.
The avarage number of phonons is given by Bose-Einstein
distribution as
_
(number of phonons) x (energy of phonon)= 

h
f ( )  h
e kT
1
Total internal energy of solid

3N 0 h
E  3N 0  h
e kT
1
Molar specific heat is given by
h

 h 
2
 E  e kT
CV     3R 
 T V  kT    2
h

 e kT  1
 
 
 Plot of Cv as a function of T

 
2
eT
CV  3R  
T    2
 where 
k
 e T  1
 
 
Cv Specific heat vanishes
exponentially at low T’s and tends to
kB classical value at high temperatures.
Area= 
The features are common to all
2 quantum systems; the energy tends
T to the zero-point-energy at low T’s
 and to the classical value of
kB Boltzmann constant at high T’s.
 Plot of Cv as a function of 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.

This range usually includes RT. From the

Cv figure it is seen that Cv is equal to 3R at
high temperatures regardless of the
3R 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
T, K same for all materials!
 Conclusion
• 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 T  1

2

• 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
3NkB  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.

• Taking into account the actual distribution of vibration

frequencies in a solid this discrepancy can be accounted using
one dimensional model of monoatomic lattice
 What is 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.
 Phonon

• The vibrational energies of molecules are quantized and

treated as quantum harmonic oscillators.
• Quantum harmonic oscillators have equally spaced energy
levels with separation ΔE = h.
• So the oscillators can accept or lose energy only in discrete
units of energy h.
• The evidence on the behaviour of vibrational energy in
periodic solids is that the collective vibrational modes can
accept energy only in discrete amounts, and these quanta of
energy have been labelled "phonons".
• Like the photons of electromagnetic energy, they obey Bose-
Einstein statistics.
PHONONS PHOTONS
• Quanta of lattice vibrations • Quanta of electromagnetic
• Energies of phonons are radiation
quantized • Energies of photons are
quantized as well

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

h
p phonon  p photon 
h
 
Problem: Two stars are observed. One has its peak output at 550 nm while the other
has its peak at 920 nm. What are the temperatures of these two stars? Assuming that
they are at the same distance from us, what are their relative total fluxes?
 Use Wien’s Law to get the temperatures of the star:

mT  2.898 10 3

mK
T1=9270 K
T2=5540 K
Flux of star 1 Lu min osity 1/4d 2 T14
Re lative flux   
Flux of star 2 Lu min osity 2/4d 2
T24
4
 9270 
Re lative flux     7.84
 5540 
Prob: Compare the average velocities of oxygen and hydrogen
molecules on the surfaces of the Earth, Moon and Mercury with
the escape velocities from these bodies. Assume that the surface
temperature of the Earth is 290 K, the Moon is 300 K, and
Mercury is 550 K.

Mearth=5.97×1024 Kg Rearth=6380 Km
Mmoon=7.35×1022 Kg Rmoon=1740 Km
Mmercury=3.3×1023 Kg Rmercury=2440 Km
 earth
vescape  1.12 104 m / sec
2GM moon
vescape  2.37 104 m / sec
vescape 
R v mercury
escape  4.25 10 m / sec
4

2kT
vthermal  mO2  2 16 1.67 10 27 kg  5.37 10 26 kg
m mH 2  3.34 10 27 kg

Tearth  290 K Tmoon  300 K

vO2  3.87 10 2 m / sec vO2  3.93 10 2 m / sec
vH 2  1.55 103 m / sec vH 2  1.57 103 m / sec