Statistical Mechanics and Thermodynamics of Simple Systems

Handout 6
Partition function
The partition function, Z, is dened by

Z=

eEi

(1)

where the sum is over all states of the system (each one labelled by i).
(a) The two-level system: Let the energy of a system be either /2 or /2. Then
Z=

Ei

/2

=e

+e

/2

= 2 cosh
.
2

(2)

(b) The simple harmonic oscillator: The energy of the system is (n + 21 )

h where n =
0, 1, 2, . . ., and hence
Z=

Ei

h
(n+ 12 )

=e

12
h

n=0

e 2 h
,
=
1 eh
1

n
h

n=0

(3)

Using the partition function to obtain functions of state

The table below lists the thermodynamic quantities derived from the partition function Z.
Function of state

d ln Z
d
kB T ln Z

U
F
S
p

Statistical mechanical expression

=
=

F
T

F
V

)
V

U F
T

kB ln Z + kB T
(

)
T

kB T

ln Z
V

= U + pV

kB T T

ln Z
T

)
T

ln Z
T

G
CV

= F + pV = H T S
=

U
T

+V
V

kB T ln Z + V

ln Z
V

[ (

ln Z
kB T 2
T

+T
V

ln Z
V

) ]
T

2 ln Z
T 2

) ]
T

) ]
V

You probably only need to remember the first two; the others can be quickly worked out.

U h

k T h

The internal energy U , the

entropy S and the heat capacity CV for (a) the twostate system (with energy
levels /2) and (b) the
simple harmonic oscillator
with angular frequency .

S k

S k

k T

CV/kB

k T h

CV/kB

k T

k T

k T h

Combining partition functions

Suppose the energy contains two independent contributions a and b with energy levels Eia and
Ejb , respectively, then
Z =

e(Ei +Ej )
a

= Za Zb ,

(4)

i.e. the product of the partition functions for the a and b systems. The generalization to more
independent contributions is obvious: Z = Za Zb Zc . . ..
Following from this, if Z(1) is the partition function for one system, then the partition function
for an assembly of N distinguishable systems each having exactly the same set of energy levels
(e.g. N localized harmonic oscillators, all with the same frequency) is
Z(N ) = Z N(1).

(5)

If the N systems are indistinguishable (e.g. an ideal gas of identical atoms or molecules) then
Z(N ) =

Z N(1)
.
N!

(6)

Example: the spin 12 paramagnet

In quantum mechanics, a particle with spin angular momentum equal to 12 , placed in a magnetic
eld B along the z direction, can exist in one of two eigenstates:
| , with angular momentum parallel to the B eld, and hence magnetic moment along
z equal to B (costing an energy +B B).
| , with angular momentum antiparallel to the B eld, and hence magnetic moment
along z equal to +B (costing an energy B B).
2

Here B = e
h/2m is the Bohr magneton and we have used the fact that energy= B, and
also that for a negatively charged particle (the electron) the angular momentum is antiparallel
to the magnetic moment.
Therefore, one spin 12 particle behaves like a two-state system, with the two states having
energies E = B B, and the single-particle partition function is simply
Z(1) = eB B + eB B = 2 cosh (B B) .

(7)

A spin 12 paramagnet is an assembly of N such particles which are assumed to be noninteracting, i.e. each particle is independent and does its own thing.
The N -particle partition function, treating the spin- 12 particles as distinguishable, is given by
Z(N ) = Z N(1) = [2 cosh (B B)]N ,

(8)

F = kB T ln Z(N ) = N kB T ln [2 cosh(B B)] .

(9)

and hence F is given by

We can work out the total magnetic moment of the paramagnet by computing
(

F
=
B

= N B tanh(B B).

(10)

The behaviour of , given

by eqn (10), is shown in the
gure on the left.
N

The magnetization M is the magnetic moment per unit volume, so

N B
M=
=
tanh(B B).
(11)
V
V
The magnetic susceptibility
is dened by M = H where H is a small applied eld, or
(
)
M
more formally = H . When B B 1 we can use tanh x x for x 1 to nd that
T

N 2B B
.
V kB T

(12)

By denition, B = 0 (H + M) = 0 (1 + )H for a paramagnet. For a weakly magnetic

material (like a paramagnet) 1, and therefore

N 0 2B
0 M
=
.
B
V kB T

(13)

1
.
T

(14)

This yields Curies law:

ATB
Michaelmas 2011