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THERMODYNAMICS
Eren ANGA
1274927
Cv= T (S / T )V = ( U / T )V
The experimental facts about the heat capacity of solids are these:
1. In room temperature range the value of the heat capacity of nearly all monoatomic
solids is close to 3Nk, or 25 J mol-1 deg -1.
2. At lower temperatures the heat capacity drops rapidly and approaches zero as T 3
in insulators and as T in metals.If metal becomes semiconductor, the drop is faster
than T. [1]
U N n
N
e
1
/
Eqn. 3
CV
e /
/
1) 2
(e
kT and kT
e 1 kT
Eqn. 4
Nk
3 N
3 NkT 3RT
kT
kT and
e kT 1
U 3 N e
kT
kT
C 3 Nk
Eqn. 6
3R
kT
E
T
Therefore, it can be seen that Einstein model succesfully predicts that C decreases with
decreasing T. However, exponential decrease is not observed; if low frequencies are
present, then will be small, much smaller than kT even at low temperatures; C will
remain at 3kT to much lower frequencies and the fall off is not as dramatic as predicted
by the Einstein model.
3.DEBYE MODEL
Debye model uses wide spectrum of frequencies to describe the complicated pattern of
lattice vibrations. It is assumed that hypothetical oscillators generate simple sine waves
throughout the crystal and these will displace the atoms away from their equilibrium
positions by an amount equal to the amplitude of the sine wave at that point. If whole set
of such oscillators generates sine waves of certain frequencies and amplitudes, then it can
be predicted that the superposition of such waves will simulate the complicated pattern of
the actual atomic vibrations. The distribution of oscillators is quasi-continuous in hence
integration can be used instead of summation. [1]
Eqn. 7 E ( ) k (e
k
kT
1)
N ( ) E ( )d
n i 1, 2, 3, .......
2
u x, k
L
= 2L, k=/L, n=1
u x, k
1
u x, k
u x, k
2
u x, k
3
4
6
u x, k
3
0.5
Figure 1
s
k
V
3
where V=L3 is the sample volume. The density of k states is uniform in k space and
depends only on the sample size. For large samples, k can be taken as a continuous
variable rather than as a discrete quantity.
Eqn. 11
g i (k)dk =
1
V
Vk 2 dk
.
4 k 2 dk 3 =
8
2 2
The density of states for a mode i in terms of frequency, g i(), may be obtained using the
linear dispersion relation valid for long-wavelength acoustic modes, giving[3]
Eqn. 12
g i ( )d =
V 2
d ,
2 2 v 3i
where vi is an appropriate sound velocity for mode i. However, three acoustic modes, one
longitudinal (LA) mode and two degenerate transverse (TA) modes, can propagate in
continuous elastic media, and so the total vibrational density of states is given by
Eqn. 13
3V 2
g( )d =
d
2 2 v 3o
where vo is an appropriate average of the LA- and TA-mode velocities. This quadratic
frequency dependence is the so called Debye density of vibrational states.
Eqn. 15
3V D 2
3N =
d ,
2 2 v 3o 0
the Debye frequency is given by
Eqn. 16
1
6 2 N
vo .
dS
V
8 3
dS
V
8 3 v g
dS
4k 2
vg k
Eqn. 18
V
V 2
2
N ( ) 3 4 k
, (see Eqn. 12)
8 v g
2 2 v g 3
Eqn. 19
max
3
V max
6 2 v 3g
N ( )d N
0
3
max
6 N 2 3
vg
V
Eqn. 20
U N ( )E( )d
V 2
2 2 v3g
V
2 3
2 v g
kT
max
3
e
kT
d
1
kT
; d =
dZ
kT
Eqn. 21
3 Z max
V kT kT
U
2 2 v 3g
Z3
dZ
eZ 1
Eqn. 22
3
max
6 2 Nv 3g
V
Eqn. 23
4
3N kT
U 3
max 3
Z max
Z3
dZ
eZ 1
Eqn. 24
max
k
This is called as Debye temperature
Eqn. 25
T
U 3N kT
3 Z max
Z3
dZ
eZ 1
U 9 N kT
D
3 Z max
Z3
dZ
eZ 1
V
U 2 3
2 v g
max
3
e
d
1
kT
Eqn. 28
max
-
kT 2
dU
V
dT 2 2 v 3g
e kT 3
2
kT 2
V 1
2 2 v 3g
e kT 4
2 kT
kT 2
max
3N
3
max
kT
kT
kT
Z max
eZ Z 4
e
0
dZ
Eqn. 29
CVD
3Nk
D
3 Z max
Z4 eZ
e
0
dZ
Debye specific heat capacity for a single acoustic branch. However, there are three
branches, i.e. two transverse acoustic and one longitudinal acoustic branch. The total
specific heat is therefore [3]:
Eqn. 30
CV D
9Nk
D
3 Z max
Z4 e Z
e
0
dZ
At low temperature
Eqn. 31
T << D
Let Zmax
Z3
4
dZ
eZ 1
15
Eqn. 32
3NkT 4 T
U
5
D
3Nk 4 4
T
5D3
Eqn. 33
CVD
T
dU
12 4
Nk
dT
5
D
Eqn. 35
CV D
9Nk
D
3 Z max
3 Z max
Z4
dZ
Z2
Z dZ
9Nk
9Nk
Z3max
3
3Nk
CONCLUSION
For sufficiently low temperatures, the Debye approximation should be quite good, as here
only long wavelength acoustic modes are excited. These are just the modes that may be
treated as in elastic continuum with macroscopic elastic constants. The energy of short
wavelength modes is too high to be populated at low temperatures.
REFERENCES
[1] Charles Kittel, Solid State Physics, 1976, John Wiley & Sons Inc.
[2] http://images.google.com.tr/images?svnum=10&hl=tr&lr=&q=heat+capacity+vs+temperature
[3] Introduction to Lattice Dynamics, Martin T. Dove, Cambridge topics in mineral physics and
chemistry lecture notes
[4] http://en.wikipedia.org/wiki/Debye_model