7.E.

Heat Capacity Of A Debye Solid

Consider a simple crystalline solid with one atom at each lattice site.
Since the size and shape of the solid are fixed macroscopically, the motion of the
atoms must be restricted to oscillations about their equilibrium positions.
The degrees of freedom of such vibrations is 3N , where N is the number of atoms.
If the amplitudes of the vibrations are small enough, the oscillations become
harmonic, i.e., the potential energy is quadratic in atomic displacements. Thus, the
atomic vibrations of a solid can be approximated as a set of 3N coupled harmonic
oscillators.
By means of a transformation into the so-called normal coordinates, the vibrations
can be de-coupled into independent normal modes.
Typical measured values of the heat capacity of monatomic solids are shown in Fig.
7.2. At high temperatures, CV approaches a constant value of 6 cal/K mole, in
agreement with the classical theory. For low temperatures, CV drops as T 3 , which
can only be explained in terms of quantum theory.
The Debye theory is a quantum theory of harmonic oscillations in a continuum.
According to classical elastic theory, there are 2 types of waves governed by the wave
equations
1 2
2
2 2 uT r , t 0
cT t

uT 0

transverse, doubly degenerate

1 2
2
2 2 u L r, t 0
cL t

uL 0

longitudinal

where c is the phase velocity. The propagating modes thus obey linear dispersion
i ci k
i L, T
and are called sound waves.

Let the solid be a rectangular lattice of sides Lx , Ly , Lz . The normal modes are
standing waves which vanishes at the surfaces. This means the allowable wave
vectors are

ki

ni
Li

where N i

where i x, y , z and ni 1, 2,L , N i

(a)

Li
, with ai being the lattice spacing, is the number of sites in the ith
ai

direction. Thus, the total number of sites is N N x N y N z . With each site having 3
degrees of freedom, the total degrees of freedom is 3N.
In the quantized version of the theory, the hamiltonian is
1

H
hi k nk ,i
(7.62)

i L ,T1 ,T2 k
where the sum over k involves N modes for each branch i. The partition function is

Z N T TrN exp hi k nk ,i
2

i L ,T1 ,T2 k

exp h k
i

nk , i 0

1
nk ,i
2

1
1

exp hi k

2
1 exp hi k
i
k

i

1
1

hi k
2

2sinh

(7.63)

Hence,

1

ln Z N T ln 2sinh hi k
2

i
k

E
ln Z N

hi k
2
1 h k

i
2
1

i
k
sinh hi k
2

cosh

1
1

hi k exp hi k
1
2
2

hi k
1
2
1

i
k
exp hi k exp hi k
2
2

exp

exp hi k 1 1
hi k
exp hi k 1 2

hi k
2 exp hi k 1

(7.64)

nk ,i hi k
2

where the average occupation of the mode k ,i

1
(7.65)
exp hi k 1
is called the Planck's formula.
The sum over k can be approximated by an integral
nk ,i

dk k
k

where the density of states in k-space, k , can be calculated from eq(a) as

Lx Ly Lz

V
3

so that
V

d 3k

ki 0

where the condition ki 0 from eq(a) restricts the integration to the 1st quadrant.

, we have
c
V
k f 3 d 3k f 2V 2 dk k 2 f
ki 0

Using k

V
d 2 f
2 3
2 c

(b)

where we've used the fact that integration of the angular part over the 1st quadrant
gives
1

d d

8
2
1st Q
Summing over the branches gives
V
f i i 2 3 d i i2 f i i

i
k
i 2 ci
For the special case that f i f , we have


1 V
f c 2 d f

3
i

3V
d 2 f
2 2 c 3

where

3
1
2 1
3 3 3
3
c
cT cL
i ci
To restrict the total number of modes to 3N, we must introduce a cutoff (Debye)
frequency D so that
3V
3N
2 2 c 3

3
d 2 V 2 D 3
2 c

6 2 N
D c

(7.68)

1/ 3

c kD

(7.69)

Defining the density of states in -space by

d g
i

we have
g

9N 2
3V
2

D3
2 2 c 3

(7.70)

Eq(7.64) thus becomes

E

n h
2

d g
0

(7.71)

where
n

1
exp h 1

With the help of (7.70), we get

9N h D
1

E 3 d 3 n
D 0
2

9 N h D4

D3 8

The heat capacity is therefore

exp h 1

(7.72)

CN

9Nh
D3 k BT 2

h 4 exp h

exp h 1

5 xD

9 N h2 k BT
3
D k BT 2 h

k T
9 Nk B B
hD
T
9 Nk B
TD

dx

3x
D

dx
0

3x
D

dx
0

x 4e x
x

x 4e x
x

x 4e x
x

For low T, we have xD . Using

dx
0

x 4e x
x

4 4
15

we get
T
12 4
CN ;
Nk B
5
TD

which is the famous Debye T 3 rule.

(7.74)

where

h
k BT