Solid State Physics

PHONON HEAT CAPACITY

Lecture 10

A.H. Harker
Physics and Astronomy
UCL
Specific Heats
To recapitulate:
• Lattice vibrations, in the harmonic approximation, described as
normal modes of the crystal;
• Each normal mode has the same Hamiltonian as a harmonic os-
cillator;
• The energy in each normal mode k is (nk + 12 )~ωk ;
Calculate the specific heat, by adding the contributions of all the
modes.
• Assume a continuous spread of frequencies/energies
• Find how many normal modes there are in a given range of fre-
quency
• Remember specific heat of harmonic oscillator of frequency ω
• Integrate over ω

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4.3 Phonon Density of States
4.3.1 One Dimension - g(k)
Take crystal of length L, and impose periodic boundary conditions, so
that for a wave
exp(ikx) = exp(ik(x + L)),
so
exp(ikL) = 1,
or
2π
k=n ,
L
where n is an integer. The allowed states are uniformly distributed in
reciprocal space (k-space) with spacing 2π/L.

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The density of states is the inverse of the spacing,
L
g(k) = .
2π
The number of allowed states with wavevectors between k and k + dk
is g(k) dk. Note that if there are N unit cells so that L = N a the total
number of allowed states in the Brillouin zone is
Z π/a
L π L
g(k)dk = × 2 = = N.
−π/a 2π a a
The number of allowed states in the Brillouin zone is equal to the
number of unit cells in the system. N.B. unit cells, not atoms. More
atoms → more degrees of freedom → more branches of the spectrum.

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4.3.2 Assumption of Continuous Energy
How closely spaced are the energy levels? Suppose the crystal is
0.01 m long. Then the spacing between k values is ∆k = 2π/L =
200π m−1. If the sound wave speed is v = 5000 m s−1 then on the
acoustic branch the minimum angular frequency is 0 and the next
is ∆ω = v∆k = 5000 × 200π = 106π rad s−1. This is small enough
compared with the maximum frequency (about 1013 rad s−1) that re-
placing a sum over discrete frequencies with an integral is a good
approximation.
The energy spacing is ∆E = ~∆ω ≈ 3 × 10−28 J = 2 × 10−9 eV.

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4.3.3 One Dimension: g(E)

Go from evenly spaced allowed values of k to, in general, unevenly

spaced values of energy. Note that positive and negative k have same
E.

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Define the density of states in frequency: number of allowed states
between ω and ω + dω is g(ω) dω. This must be the same as the
number in the region of k-space containing states in that frequency
interval, so in 0 < k < π/a
g(ω) dω = g(k) dk,
or
dk dω
g(ω) = g(k) = g(k)/ .
dω dk
Allowing also for the states with negative k we get in one dimension
L dk
g(ω) = 2 .
2π dω
dω
= vg ,
dk
the group velocity of the wave. Non-dispersive system vg is constant,
so
L
g(ω) = = constant.
πvg
Monatomic chain
ω = ω0 sin(ka/2),
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so
aω0
vg = cos(ka/2)
2 q
aω0
= 1 − sin2(ka/2)
2 q
aω0
= 1 − ω 2/ω02
2q
a
= ω02 − ω 2.
2
and then
2L
g(ω) = q .
πa ω02 − ω 2

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One-dimensional density of states for real monatomic structure, non-
dispersive system (Debye model), and real diatomic structure.

Note that in one dimension we have singularities whenever the ω(k)

curve is flat.

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4.4 Three dimensions – g(E)
Apply periodic boundary conditions along x, y and z. The number
of states in the reciprocal space volume dkxdky dkz is then
Lx Ly Lz V
3
dkxdky dkz = 3 dkxdky dkz ,
(2π) 8π
for crystal volume V . Now assume that the crystal is isotropic – ω
depends only on magnitude of k, not its direction. Then
dkxdky dkz = 4πk 2dk
and the number of states with modulus of wavevector between k and
k + dk is
V V
g(k)dk = 3 4πk dk = 2 k 2dk
2
8π 2π
Here we’ve accounted for all directions, so no extra factor of 2 as in
one dimension when going to g(ω).

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But we do have to include all the modes (acoustic, optic, longitudinal,
transverse), each with its own dispersion relation, so
V X 2 dωs
g(ω) = 2 k(ωs) / ,
2π s dk
where s denotes the mode. Non-dispersive system If we assume that
ωs(k) = vsk,
i.e. the sound speed does not depend on frequency, we have
ω
k(ωs) = ,
vs
and
dk 1
= ,
dωs vs
so
V X ω2
g(ω) = 2 3
.
2π s vs

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If we define an average sound speed v by
 
1 1
3
= 3
,
v vs
where h...i denotes an average. e.g.
" #
1 1 1 2
3
= 3
+ 3 ,
v 3 vL vT
then
V Sω 2
g(ω) = 2 3 .
2π v
Here S is the number of branches in the phonon spectrum – 3 for a
monatomic 3-D solid.

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4.4.1 Special case - single frequency
If we assume (the Einstein model)

we get a delta-function density of states.

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N.B. Einstein model can be used as model of narrow optical branch
of phonon spectrum.
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Real density of states: complicated structure – no singularities (con-
trast 1-D), but discontinuities in slope.

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4.4.2 Quantised Simple Harmonic Oscillator
(Revision of 2B28) For an oscillator of frequency ω in its nth energy
level the partition function is

∞  
X En
Z = exp −
kB T
n=0
∞  
X (n + 1/2)~ω
= exp −
kB T
n=0
1
=  
2 sinh 2k~ωT
B
1
=  
2 sinh β~ω2

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 ∂ ln Z
hEi = −
∂β
1
= (hni + )~ω,
2
The crucial result is the mean occupation number of the nth level:
1
hni = ,
exp(~ω/kBT ) − 1
for Bose-Einstein statistics.

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Higher frequency → lower occupancy at given temperature.

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Free energy
F = −kB ln(Z)
  
~ω
= kBT ln sinh
2kBT

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Entropy The decrease in free energy with T is due to an increase in
entropy. at p = 0
E−F
S= .
T

Increase T , increase S: more displacement from equilibrium position

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means more disorder.

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Specific heat:
∂E
C= .
∂T

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• low T : exponential dependence C ∝ T −2 exp(−~ω/kBT
• intermediate T ≈ ~ω/3kB: steep rise in C
• high T > ~ω/kB: C saturates to classical result, C = kB per oscil-
lator.
• C universal function of T /Θ, where Θ = ~ω/kB

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