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3.3. Summary
4. The Debye Model, 1912
4.1. The Debye Approach
4.2. The Density of Modes
4.3. Density of Modes and the Debye Model
• Evaluation of the Debye Integral
4.4. The Debye Model at Low Temperture
1. Photons
1.1. Blackbody Radiation
All objects emit electromagnetic radiation, the peak wavelength is a
function of temperature. In most cases the radiation is not in thermal
equilibrium with matter. Consider an opaque enclosure whose walls
are maintained at a constant temperature T . The radiation and walls
will reach thermal equilibrium and the radiation will have definite
properties.
To study the properties of this equilibrium radiation we can imag-
ine cutting a small hole in the enclosure. If the hole is small enough, it
will not disturb the radiation in the cavity. Radiation will be emitted
through the hole and this radiation will have the same properties as
the cavity radiation. This radiation will also have the same properties
as the radiation emitted by a perfectly black body at the same tem-
perature as the enclosure T . Why? A perfectly black body absorbs
all radiation falling on it – the hole behaves in the same way – all
incident radiation will enter the hole.
Thus, the terms cavity radiation and blackbody radiation are syn-
onymous. We will analyze the situation by treating blackbody radia-
tion as a gas of photons.
X ∞
∞ X X
Z= ... e−βn1 ²1 e−βn2 ²2 e−βn3 ²3 . . .
n1 =0 n2 =0
à !à ! à !
X X X
−βn1 ²1 −βn2 ²2 −βni ²i
Z= e e ... e
n1 n2 ni
and so we write this as
∞
Y X
Z= e−βnj ²j .
j=1 nj
Now, if we let x = e−β²j , and we see that we have the geometric series
1 + x + x 2 + x3 + . . .
Now
1
1 + x + x 2 + x3 + . . . = if x < 1.
1−x
1
x = e−β²j = β²j
e
(Convince yourselves that this holds, you might use ²j = ~ω.) So we
can rewrite our photon partition function as
∞
Y 1
Zph (T, V ) = −β²j
j=1
1 − e
In principle this gives us all the physics. To make any further progress,
we need to calculate the mean occupation number, we know how to
do this, but we haven’t actually made the calculation.
Now
µ ¶
1 ∂Z 1 ∂ X −β(n1 ²1 +n2 ²2 +n3 ²3 +...)
− = − e
β ∂²i β,²j β ∂²i n ,n ,...
1 2
1 X
= − (−βni )e−β(n1 ²1 +n2 ²2 +n3 ²3 +...)
β n ,n ,...
1 2
X
= ni e−β(n1 ²1 +n2 ²2 +n3 ²3 +...) .
n1 ,n2 ,...
∞
Y 1
ln Zph = ln
j=1
1 − e−β²j
∞
X
= (ln 1 − ln(1 − e−β²j ))
j=1
X∞
= − ln(1 − e−β²j )
j=1
The density of states f (ω)dω depends only on the size of the container.
This means that the photon density and the energy density in the
cavity are uniform. So we write
dEω ~ω 3 dω
= 2 3 β~ω = u(ω, T )dω,
V π c (e − 1)
where
u(ω, T ) = energy/unit volume/unit frequency range
= spectral density
~ω 3
= .
π 2 c3 (eβ~ω − 1)
This is the Planck radiation law. A plot of u(ω, T ) against (usually
inverse) wavelength would show a different peak for each temperature.
So for every temperature there is a unique frequency that is the
peak emission frequency. At 6000 K, the peak lies at the edge of the
Now, let x = β~ω, and note that ω = ωmax , we are locating the
maximum. Thus rewriting, we get
3(ex − 1) = xex .
To find the value of x satisfying this equation, we can use numerical
or graphical methods.
What value of x satisfies
3(ex − 1)
= x.
ex
One way to approach this is to guess an answer and iterate, let’s try
it with an initial guess of x = 3. Then we find
3(e3 − 1)
= 2.8506, this becomes our new guess
e3
= 2.8266
= 2.8824
..
.
= 2.822.
where
Z∞
x3 dx π4
= , a simple contour integral
ex − 1 15
0
leading to
π2 k4 T 4 E
U (T ) = = = aT 4 .
15c3 ~3 V
This is the Stefan-Boltzmann law, where σ = 4c a is the Stefan-Boltzmann
constant.
4 π2 k4 V T 3
µ ¶
∂E
=
∂T V,N 15 c3 ~3
so, provided N, V are constants, we can write
4 π2 k4 V T 3
dE = dT
15 c3 ~3
dE 4 π2 k4 V T 2
dS = = dT
T 15 c3 ~3
4 π2 k4 V
Z
S= T 2 dT
15 c3 ~3
µ ¶3
4 2 4 T
S= π k V + constant.
45 c~
Now, as we have previously noted, by the strong form of the third law
of thermodynamics, limT →0 S = 0 resulting in
µ ¶3
4 2 4 T
S= π k V .
45 c~
2. Phonons
The energy of elastic waves is quantized – just as the energy of electro-
magnetic waves in a cavity is quantized. When we talk about phonons,
we are talking about the allowed vibrational modes in solids. The en-
ergies of these lattice vibrations are quantized because only certain
modes of vibration are allowed. Thus, we can treat elastic vibrations
in solids as particles or waves. The energy in a vibrational mode can
be treated as a quantum mechanical oscillator of the same frequency.
We can develop our treatment based on the properties of quantum
mechanical oscillators. Ultimately, we shall calculate heat capacities
— before embarking on those calculations, let’s look at the heat ca-
pacity of solids.
e−β~ω/2
Z=
1 − e−β~ω
β~ω
ln Z = − − ln(1 − e−β~ω )
2
so
∂ ln Z
hEi = −
∂β
~ω ∂
= + ln(1 − e−β~ω )
2 ∂β
~ω 1
= + ~ωe−β~ω
2 1 − e−β~ω
~ω ~ω
= + β~ω
2 e −1
Now, comparing this with E = (s + 1/2)~ω, we see that we can write
µ ¶
1
E = hsi + ~ω
2
where
1
hsi = .
e~ω/kT
−1
We can interpret this as the average occupancy of a photon mode ω.
As we have already seen (when we derived it directly for photons) this
is the Planck distribution.
Then using
N ~ω
E=
e~ω/kT − 1
and µ ¶
∂E
Cv =
∂T v
We find
∂ ~ω/kT
Cv = N ~ω [e − 1]−1
∂T
~ω
µ ¶
~ω/kT −2 ~ω/kT
= N ~ω(−1)[e − 1] e − 2
kT
¶2
~ω e~ω/kT
µ
= Nk .
kT (e~ω/kT − 1)2
This is for the one-dimensional Einstein solid. In three dimsnsions,
we replace N ny 3N , since each atom has three degrees of freedom
and we find ¶2
~ω e~ω/kT
µ
Cv = 3N k .
kT (e~ω/kT − 1)2
How good is this expression? Let x = ~ω/kT , then
x 2 ex
Cv = 3N k ,
(ex − 1)2
we can then examine the behavior of this expression at high and low
temperature.
Let
x2 x3
ex = 1 + x + + + ...
2! 3!
so we have
x2 x3
x2 (1 + x + 2! + 3! + . . .)
x2 x3
.
(x + 2
2! + 3! + . . .)
This obviously goes to 1 as x → 0. This yields the classical result of
Dulong and Petit, Cv = 3N k.
3.3. Summary
Thus, in the Einstein model, the high temperature behavior is good,
the behavior at T = 0 is good, the low temperature behavior is not
If the ni were zero there would be no wave. Consider light, for any
given triplet ni , there are two polarizations, and on substituting into
the wave equation
µ 2
∂2 ∂2 ∂ 2 Ex
¶
∂
c2 2
+ 2
+ 2
Ex =
∂x ∂y ∂z ∂t2
where c is the velocity of light, we find
c2 π 2 (n2x + n2y + n2z ) = ω 2 L2 .
This determines the frequency of the mode in terms of the triplet of
integers nx , ny , andnz . Defining
n ≡ (n2x + n2y + n2z )1/2 ,
and the frequencies are given by
nπc
ωn = .
L
For cavity radiation, we could use this to write the total energy of
photons in a cavity as
X X ~ωn
E= hεi i = ~ω
.
n n
e /kT − 1
n
So ¶n D
n3
µ
3
4π = 3N
8 3 0
and µ ¶1/3
6N
nD = .
π
The average energy of an oscillator is
~ω ~ω
hEi = + ~ω/kT .
2 e −1
Now omitting the zero point energy (it doesn’t affect Cv ),
X X ~ωn
E= hεn i = ~ωn /kT − 1
n
e
and
ZnD
3 ~ωn
E= 4πn2 dn ~ω
.
8 e /kT
n −1
0
and
ZnD
3 π 2 ~c 3 1
E = (n dn) x
2 L e −1
0
ZnD ¶4
π 2 ~c x3 dx
µ
3 LkT
=
2 L π~c ex − 1
0
¶4 ZxD
3 π 2 ~c x3 dx
µ
LkT
= .
2 L π~c ex − 1
0
The upper limit of integration is
π~cnD π~cnD
xD = = 1/3 ,
LkT V kT
since µ ¶1/3
3 6N
L = V and nD = .
π
Using this in
¶4 ZxD
3 π 2 ~c x3 dx
µ
LkT
E=
2 L π~c ex − 1
0
we find
3 L3 k 4 T 4 π 4
E' .
2 π 2 ~3 c3 15
But ¶1/3 ¶3
~c 6π 2 N ~c 6π 2 N
µ µ
ΘD = , Θ3D =
k V k V
so
3 π4 V 6k 3
E = N kT 4
2 15 6N π 2 ~3 c3
4
3π 6
= N kT 4 3
2 15 Θd
3 N kT 4 π 4
= .
5 Θ3D
Then µ ¶
∂E
Cv =
∂T v
yields
¶3
12 N kT 3 π 4
µ
T
Cv = ' 234N k .
5 Θ3D ΘD
In other words Cv → 0 as T → 0 and at low temperatures Cv ∝ T 3 .
This is the Debye T 3 approximation. At high temperatures the model
yields the Dulong and Petit result. This model is “exact” at low and
high temperature and an interpolation formula in between.
At “sufficiently” low temperatures, the T 3 approximation is good.
At such temperatures only long wavelength acoustic modes are ex-
cited. These are just the modes that can safely be treated as an
elastic continuum with macroscopic elastic constants. The energy of
short wavelength modes (for which this approximation fails) is too
high for them to be significantly populated. For actual crystals, the
temperatures for which the T 3 law holds is quite low, typically ΘD /50.
As examples ΘD = 645 K for Si, in fact, let’s look at this column of
Element ΘD (K)
C 2230
Si 645
Ge 374
Sn 200
Pb 105
Note that the heavier atoms have the lowest ΘD ’s, this is because
the velocity of sound decreases as density increases.
In a later course, you will study optic and acoustic phonons. A
common practice is to model acoustic phonons with the Einstein
model being used to model the optical phonon part of the phonon
spectrum. Further discussion is beyond the scope of our course at
this point.1
1 If you really want to know more at this point refer to Kittel’s Introduction to