Solid State Physics

PHONON HEAT CAPACITY

Lecture 11

A.H. Harker Classical equipartition of energy gives specific heat of 3pR per mole,
Physics and Astronomy where p is the number of atoms in the chemical formula unit. For
UCL elements, 3R = 24.94 J K−1 mol−1. Experiments by James Dewar
showed that specific heat tended to decrease with temperature.
3

4.5 Experimental Specific Heats

Element Z A Cp Element Z A Cp
−1
J K mol−1 J K mol−1
−1
Lithium 3 6.94 24.77 Rhenium 75 186.2 25.48
Beryllium 4 9.01 16.44 Osmium 76 190.2 24.70
Boron 5 10.81 11.06 Iridium 77 192.2 25.10
Carbon 6 12.01 8.53 Platinum 78 195.1 25.86
Sodium 11 22.99 28.24 Gold 79 197.0 25.42
Magnesium 12 24.31 24.89 Mercury 80 200.6 27.98
Aluminium 13 26.98 24.35 Thallium 81 204.4 26.32 Einstein (1907): “If Planck’s theory of radiation has hit upon the
Silicon 14 28.09 20.00 Lead 82 207.2 26.44 heart of the matter, then we must also expect to find contradictions
Phosphorus 15 30.97 23.84 Bismuth 83 209.0 25.52 between the present kinetic molecular theory and practical experi-
Sulphur 16 32.06 22.64 Polonium 84 209.0 25.75 ence in other areas of heat theory, contradictions which can be re-
moved in the same way.”

2 4
Einstein’s model If there are N atoms in the solid, assume that each Limits
vibrates with frequency ω in a potential well. Then
~ω
N ~ω ~ω 2 e kB T
 
E = N hni~ω = ~ω , CV = N kB 2 .
kB T
 ~ω
k T
e B −1 e kB T −1
and  
∂E ~ω
CV = T → 0. Then e kBT >> 1 and
∂T V
2 ~ω
Now 
~ω
~ω
e kBT! → T −2e− kBT .
CV → N kB k T
 
∂ ~ω ~ω B 2
=− , ~ω
∂T kBT kB T 2 e kB T
so   ~ω
∂ ~ω k~ωT Convenient to define Einstein temperature, ΘE = ~ω/kB.
e kB T = − e B ,
∂T kB T 2
and
~ω
~ω 2 e kB T
 
CV = N kB 2 .
kB T
 ~ω
e kB T − 1

5 7

Limits
~ω
~ω 2 e kB T
 
CV = N kB 2 .
kB T
 ~ω
e kB T −1
~ω ~ω
T → ∞. Then k~ωT → 0, so e kBT → 1 and e kBT − 1 → k~ωT , and
B B
 2
CV → N kB k~ωT  1 2 = N kB.
B ~ω
kB T

This is the expected classical limit.

6 8
 • Einstein theory shows correct trends with temperature.
• For
p simple harmonic oscillator, spring constant α, mass m, ω =
α/m.
• So light, tightly-bonded materials (e.g. diamond) have high fre-
quencies.
• But higher ω → lower specific heat.
• Hence Einstein theory explains low specific heats of some elements.

Systematic deviations from Einstein model at low T. Nernst and Lin-

demann fitted data with two Einstein-like terms.Einstein realised that
the oscillations of a solid were complex, far from single-frequency.
Key point is that however low the temperature there are always some
modes with low enough frequencies to be excited.

9 11

4.6 Debye Theory

Walther Nernst, working towards the Third Law of Thermodynam- Based on classical elasticity theory (pre-dated the detailed theory of
ics (As we approach absolute zero the entropy change in any process lattice dynamics).
tends to zero), measured specific heats at very low temperature.
10 12
The assumptions of Debye theory are Taking, as in Lecture 10, an average sound speed v we have for each
• the crystal is harmonic mode
V ω2
• elastic waves in the crystal are non-dispersive g(ω) = 2 3 ,
2π v
so
• the crystal is isotropic (no directional dependence) Z ω
D V ω2
• there is a high-frequency cut-off ωD determined by the number of N = dω
0 2π 2 v 3
degrees of freedom
V ω 3
= 2 D3
6π v
6N π 2 3
ωD3 = v
V

Equivalent to Debye frequency ωD is ΘD = ~ωD/kB, the Debye tem-

perature.

13 15

4.6.1 The Debye Frequency 4.6.2 Debye specific heat

The cut-off ωD is, frankly, a fudge factor. Combine the Debye density of states with the Bose-Einstein distri-
If we use the correct dispersion relation, we get g(ω) by integrating bution, and account for the number of branches S of the phonon
over the Brillouin zone, and we know the number of allowed values spectrum, to obtain
of k in the Brillouin zone is the number of unit cells in the crystal, so ~ω
R ωD V ω2  ~ω 2 e kB T
we automatically have the right number of degrees of freedom. CV = S 0 2π 2 v 3 kB k T !2 dω.
B ~ω
In the Debye model, define a cutoff ωD by e kBT −1
Z ω
D
N= g(ω)dω, Simplify this by writing
0
where N is the number of unit cells in the crystal, and g(ω) is the ~ω k Tx ~ω
x= , so ω = B , xD = D ,
density of states in one phonon branch. kB T ~ kB T
and
D V k 2 T 2 x2
Z x
B 2 ex kB T
CV = S k B x dx
0 2π 2 ~2v 3 (ex − 1)2 ~
3 T 3 Z xD
V kB x4ex
= SkB 2 3 3 dx
2π ~ v 0 (ex − 1)2
14 16
 3 T 3 Z xD 4.6.3 Debye model: high T
V kB x4ex
CV = SkB 2 3 3 dx. T3
Z x
D x4ex
2π ~ v 0 (ex − 1)2 CV = 3N SkB 3 dx.
Remember that ΘD 0 (ex − 1)2
3 6N π 2 3 At high T, xD = ~ωD/kBT is small. Thus we can expand the inte-
ωD = v ,
V grand for small x:
so ex ≈ 1,
V 3N 3N ~3
= = and
2π 2v 3 ωD3 kB 3Θ 3
D
(ex − 1) ≈ x
and
3 3 so
CV = SkB 3N ~3 kBT R xD x4ex dx, Z x
x4ex
Z x 3
2dx = xD .
D D
kB3Θ 3
D ~
3 0 (ex−1)2 dx ≈ x
3 Rx 4 x 0 (ex − 1)2 0 3
= 3N SkB T 3 0 D xx e 2 dx. The specific heat, then, is
ΘD (e −1)
As with the Einstein model, there is only one parameter – in this case T 3 x3D
ΘD. CV ≈ 3N SkB ,
ΘD3 3

17 19

Improvement over Einstein model.

T 3 x3D
CV ≈ 3N SkB 3 ,
ΘD 3
but
~ωD ΘD
xD = =
kB T T
so
CV ≈ N SkB.
This is just the classical limit, 3R = 3NAkB per mole. We should have
expected this: as T → ∞, CV → kB for each mode, and the Debye
frequency was chosen to give the right total number of oscillators.

Debye and Einstein models compared with experimental data for Sil-
ver. Inset shows details of behaviour at low temperature.

18 20
4.6.4 Debye model: low T 4.6.5 Successes and shortcomings
T3
Z x
D x4ex Debye theory works well for a wide range of materials.
CV = 3N SkB 3 dx.
ΘD 0 (ex − 1)2
At low, xD = ~ωD/kBT is large. Thus we may let the upper limit of
the integral tend to infinity.
Z ∞
x4ex 4π 4
dx =
0 (ex − 1)2 15
so
T 3 4π 4
CV ≈ 3N SkB 3
ΘD 15
For a monatomic crystal in three dimensions S = 3, and N , the num-
ber of unit cells, is equal to the number of atoms. We can rewrite this
as  3
T
CV ≈ 1944
ΘD
which is accurate for T < ΘD/10. But we know it can’t be perfect.

21 23

Roughly: only excite oscillators at T for which ω ≤ kBT /~. So we

expect:
• Very low T: OK
• Low T: real DOS has more low-frequency oscillators than Debye,
so CV higher than Debye approximation.
• High T: real DOS extends to higher ω than Debye, so reaches clas-
sical limit more slowly.
22 24
Use Debye temperature ΘD as a fitting parameter: expect:
• Very low T: good result with ΘD from classical sound speed;
• Low T: rather lower ΘD;
• High T: need higher ΘD.

25