BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE, PILANI

FIRST SEMESTER 2024-25

Statistical Mechanics
Instructor: Tapomoy Guha Sarkar
Lecture 28-29

1 Phonons
Consider a crystal of atoms. Such a crystal consists of individual atoms are stuck in position which
gives rigidity to the lattice. The atoms however vibrate about their mean positions. The lattice then
behaves like a large number of oscillators coupled to each other.
Consider the simplest classical example of N particles, each of mass m connected by springs along a
straight line. When the particles are at rest their separation is l. If each spring has a spring constant
K = mω02 , and if y1 , y2 .y3 ..... denote the diplacements of the particles about their mean position then
the equation of motion for the pth particle is given by
d2 yp
m = mω02 (yp+1 − yp ) − mω02 (yp − yp−1 ) (1)
dt2
The set of N coupled equations are decoupled using the N normal modes of vibration. Thus the
motion of the pth particle in the nth normal mode is given by
 
pnπ
ypn (t) = Cn sin cos ωn t (2)
N +1
where the normal frequency ωn is given by
 
nπ
ωn = 2ω0 sin (3)
2(N + 1)
A general motion of the system is a suposposition of the normal modes of oscillation. When we take
the thermodynamic limit of N → ∞ and N l = L then we may write the solution in terms of a
continuous x = pl which is the position of the pth particle as
 nπx 
yn (x, t) = Cn sin cos ωn t (4)
L
There are a total of N such modes. In the thermodynamic limit the above describes a standing wave
with definite frequencies having nodes at the boundary. Defining a wave number kn = nπ/L we have
then the dispersion relation
 
kl π
ω(k) = 2ω0 sin , 0≤k≤ (5)
2 l

The ω = ω(k) relation is non-linear. The linearized dispersion may be written as

 
kl kl
ω(k) = 2ω0 sin ≈ 2ω0 (6)
2 2
The sound speed is then
cs = ω/k = ωo l (7)
The analysis can be generalized to theee dimensional crystal lattices. For N atoms there are 3N
oscilators (corresponding to vibration along three dimensions) which are coupled. The standing wave
modes are characterized by a k and ω(k). The vibrational energy of the lattice is then the sum of the
energies of the independent modes.
The quantum of electromagnetic waves in a cavity was called photon and radiation was studies using
statictics of photon distribution. The quanta of sound waves in a solid are called phonons which, takes
discrete energy ~ω. We note that the atoms in the lattice do not constitute a boson gas. They are
infact stuck to their mean positions. Elastic vibrations of atoms in the entire crystal is now replaced
by a bosonic phonon gas in the quantum picture The density of states for a gas of phonons is the
same as that of photons with two major differences
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1. The speed of light c has to replaced by the speed of sound cs .

2. The phonons have three polarization states rather than two (for photons). There are two trans-
verse polarizations (like the photon) but also a single polarization mode for the longitudinal
wave.

The density of states is therefore given by Density of states for bosons (with 3 polarization states) in
terms of ω where ω = 2πν is

3V ω 2 dω
g(ω)dω =
2π 2 cs 3
If we now consider the speeds of the transverse and longitudinal waves to be different, we shall have

V ω 2 dω
 
2 1
g(ω)dω = +
2π 2 cT 3 cL 3
Since there are N atoms in the lattice, we shall have a total of 3N modes.

2 Specific heat of solids

The Dulong and Petit law states that the molar heat capacity at constant volume CV for all solids is
equal to 3R, where R is the gas constant. This can be easily derived from the equipartition theorem.
Each atom in a lattice was considered to be vibrating as a harmonic oscillator with three vibrational
degrees of freedom. The total energy per mole is then
1
E= kT × 6NA
2
where NA is the Avagadro’s number. The molar heat capacity is then given by
dE
CV = = 3kNA = 3R
dT
Experimentally, however we know that though this is the right behaviour at very high temperatures,
CV decreases with temperature and at T → 0 we know CV → 0

2.1 Einstein’s theory specific heat

Einstein assumed that the lattice consisted of 3N one-dimensional oscillators all with the same fre-
quency He wrote the total energy as
hν
E = 3N (8)
ehν/kT −1
This gives us
2
ehν/kT

dE hν
CV = = 3N k (9)
dT kT (ehν/kT − 1)2
Defining a temerature scale for the frequency ν as ΘE = hν/k we have
2
eΘE /T

dE ΘE
CV = = 3N k (10)
dT T (e /T − 1)2
ΘE

The temperature ΘE is called the Einstein temperature. If the temperature is high that T  θE then
k T  ~ ω, and the above expression for CV reduces to CV = 3 N k, by truncating the expotentials,
thereby recovering the law of Dulong and Petit at temperatures significantly higher Einstein temper-
ature. On the other hand, if the temperature is sufficiently low that T  θE then the exponential
factors become very much larger than unity, and then
 2
θE
CV ∼ 3 N k exp(−θE /T ).
T

So, in this simple model of the solid the specific heat approaches zero exponentially as T → 0.
In reality, the specific heats of solids do approach zero but not exponentially fast as suggested by
Einstein’s model when T → 0. The experimentally observed low temperature behaviour CV ∝ T 3
remains unexplained in Einstein’s theory. The reason for the discrepancy is rooted in the obvious crude
approximation that all the modes have the same frequency. In fact, long wavelength/low frequency
modes are much harder to freeze out (because the spacing between quantum energy levels, ~ ω, is
smaller). These long wavelength modes make a significant contribution to the heat capacity even at
very low temperatures.
2.2 Debye’s Theory of Specific heat
We now consider that phonons with different mode frequencies contribute to the specific heat. However
there is an upper cutoff to the number of modes given by 3N This limits the maximum frequency that
phonon modes can take. We call this upper cutoff on frequency as ωD .Thus
Z ωD
g(ω)dω = 3N (11)
0
Writing
3V ω 2 dω
g(ω)dω =
2π 2 cs 3
we have ωD
3V ω 2 dω
Z
= 3N
0 2π 2 cs 3

6π 2 cs 3 N
∴ ωD 3 = (12)
V
Now average energy is given by
ωD ωD
ω 3 dω
Z Z
g(ω) 9~N
Ē = (~ω) dω =
0 e ~ω/kT −1 ωD 3 0 e~ω/kT − 1
dĒ
Recall from thermodynamics that specific heat is given by CV = dT

ωD
ω 3 ~ω e~ωβ dω
Z
1 9~N
CV =
kT 2 ωD 3 0 (e~ωβ − 1)2
~ωD
Changing variable to x = ~ωβ , ΘD = k is called the Debye temperature.

ΘD /T
9N kT 3 x4 ex dx
Z
CV =
ΘD 3 0 (ex − 1)2
CV (T ) = 3N kfD (ξ0 )
where
ξ0
x4 ex dx
Z
3
fD (ξ0 ) =
ξ03 0 (ex − 1)2
and ξ0 = ΘD /T .
Integrating by parts

ξ0
ex dx 12 ξ0 x3 dx
Z Z
3
fD (ξ0 ) = 3 x4 |ξ00 + 3
ξ0 0 (ex − 1)2 ξ0 0 (ex − 1)
Z ξ0
3ξ0 12 x3 dx
fD (ξ0 ) = − ξ0 + 3
e − 1 ξ0 0 (ex − 1)
CASE I : T /ΘD >> 1 :

(ex − 1)2 → (1 + x − 1)2 → x2

Hence after solving the integral and subtituting value of x, we get the high temperature limit of specific
heat

ΘD /T ΘD /T
9N kT 3 x4 dx 9N kT 3
Z Z
CV = → x2 dx ≈ 3N k
ΘD 3 0
x
(e − 1) 2
ΘD 3 0

CASE II : T /ΘD << 1 :

CV (T ) = 3N kfD (ξ0 )
where ∞
x3 dx
Z
12
fD (ξ0 ) →
ξ03 0 (ex − 1)
Thus 3
12 π 4 12π 4

T
CV → 3N k 3 = Nk (13)
ξ0 15 5 ΘD
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This is the famous T 3 law for specific heat of solids at low temperatures.
The Debye’s theory parametrizes the ignorance of the microscopic physics in terms of just one measur-
able parameter. This is typical of effective field theories. The long-wavelength physics is described in
terms of a continuum of modes The description fails at short wave lengths and thereby an UV cutoff
scale (here the Debye frequency) is imposed. The physics at such short wavelengths is parametrized
in terms of a few parameters.