Statistical Physics: PHYC30017

Dr. Andy Martin (Room 613)

Lecture 12
Specific Heat of Solids:
The Einstein Solid

Review of lecture 11
Paramagnets
M/(N )
1.0

Ideal paramagnet

B
B

0.5

!4

!2

!0.5

!1.0

Spin j paramagnet

Ej = jgB B
Ej+1 = (j 1)gB B

Ej1 = (j + 1)gB B
Ej = jgB B

Todays lecture
References AV Chapters III-2.4 and IV-3

ZN = (Z1 )N

Breakdown of the Einstein model

Specific heat of solids: introduction

Observation
In the 19th century the value of CV/N, the specific heat per particle, of
most solids was known to follow the Dulong-Petit law
CV = 3kN
Harmonic oscillator model
The energy of a single oscillator is
p2
1 2 2
E=
+ x
2m 2

and there are thus six quadratic degrees of freedom, giving an energy per
particle of 6kBT/2, and a specific heat/particle of 3kB.

Beyond Dulong-Petit
By the end of the century it became apparent that:
Some solids, e.g. diamond, had specific heats below the Dulong-Petit
value.
At lower temperatures the specific heat of all solids reduced, and
seemed to go to zero as T 0.

Einstein
From Quantum mechanics + Boltzmann's probability distribution, we
expect that the probability of an harmonic oscillator being excited to the
first excited state is of order exp{-h/(2kBT)}, which goes to zero as T
0, so we can understand the temperature dependence of the specific
heat.

Einstein inverted this argument to show that the decrease of the specific
heat of solids at low temperatures was an example of quantum mechanics
at work. This was the first example of the application of quantum
mechanics to matter.

The Einstein solid

Einstein's model of a solid - each of the N ions is in a 3d harmonic
oscillator well with the frequency - all ions have the same frequency

ZN = (Z1 )N

Z1 is the partition function of a single harmonic oscillator in 3

dimensions, with energy levels:

!n = !(nx + ny + nz + 3/2)

The partition function

Z1

The partition function, for one site

!
#3
#3 !
!
2kT
"
e
=
e!(n+1/2)/(kT )
=
!

kT
1e
n=0
$
'3
1
% ! &
=
2 sinh 2kT
The partition function, for N sites

Z = ZN = (Z1 )

1
" ! #
=
2 sinh 2kT

$3N

The mean energy

ln Z
1 Z
1
U =
=
= 3N ! coth

Z
2

Define the Einstein temperature:

E = !/kB

1
!
2

"

U = (3/2)N kB E coth(E /(2T ))

High temperature: T >> E
U = 3N kB T

1 x
lim cothx = + ...
x0
x 3

Low temperature: T << E

U = 3N kE /2 = 3N !/2

lim cothx = 1

Specific heat
U
CV =
= 3N kB
T

E
2T

"2

1
sinh2 (E / {2T })

Low temperature: T << E

1
4
2x
lim
=
lim

4e
x sinh2 x
x (ex ex )2
!
"2
E
eE /T
CV = 3N k
T
The specific heat takes the
High temperature: T >> E Dulong-Petit value at high T.
The specific heat vanishes at
x3
lim sinhx = x + ...
low T, in agreement with the third
x0
6
law.
CV = 3N kB

Comparison with experiments

Check entropy
F

=
=

"

E
2T

#$

kB T ln Z = 3N kB T ln 2 + ln sinh
!
$
F

T
!
"
#
"
#$
E
E
E

3N kB ln 2 + ln sinh
coth
2T
2T
2T

As T 0
!

E
E
S 3N k
ln 2
2T
2T

"
+ ln 2 0

Einstein to Debye
The discrete energy levels of quantum mechanics, with the Boltzmann
factor determining probabilities, gives freezing of degrees of freedom
and the third law of thermodynamics.
New experiments showed that the behaviour at low temperatures was not
well described by Einstein's theory, which gave an exponential decrease
to zero, much faster than observed. The data for insulators fit T3 law at
low temperatures.

Debye theory

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