Derive the the generalized partition function for fermions (Fermi-Dirac particles) and

bosons (Bose-Einstein particles).

Solution:

3 Types of Statistics:

 Classical or Maxwell-Boltzmann statistics: Any particle can be in any state and an over-
all factor of 1/N! for indistinguishability is added ad hoc to the number of states  = 1/N!
1
1 (microcanonical ensemble) or to partition function: Z= ∑ e− β E (canonical
k

N! k
ensemble).
 Bose-Einstein statistics: Multiple particles can occupy the same state. But when they do,
there is only one state with the multiple particles in it. No N! is added: Z=∑ e− β E .
k

 Fermi-Dirac statistics: No two particles can occupy the same state. No N! is added:
Z=∑ e− β E . k

To compare the three statistics, consider 2 particles with 3 possible single particle states with
energies 1, 2, and 3.

For Maxwell-Boltzmann statistics, the particles are treated as distinguishable for counting
states, and the 1/N! is added at the end. Denoting the two particles are A and B, the possible
states and canonical partition function (with =1/kBT):

1 AB A A B B
2 B A AB B
3 B A A A AB

1 −2ε β −2ε β −2ε β

Z MB=
2!
[ e + e + e + 2e−( ε + ε ) β +2 e−(ε +ε ) β + 2e−( ε +ε ) β ]
1 2 3 1 2 1 3 2 3

The ½! Is the identical particles factor. The two particles are treated differently when
constructing the partition function, then divide by N!.

For Bose-Einstein statistics, the possible states and canonical partition function are:

1 AA A A
2 A AA A
 3 A A AA

−( ε 1 +ε2 ) β − ( ε 1+ ε 3 ) β − ( ε 2+ ε 3) β
Z BE=e−2 ε β + e−2 ε β + e−2 ε β + e
1 2 3
+e +e

Note that particles are identical, hence AA = BA =AB is one state. No N! is necessary.

For Fermi-Dirac statistics, the possible states and canonical partition function are:

1 A A
2 A A
3 A A

− (ε1 +ε2 ) β −( ε1 +ε3 ) β −( ε2 +ε3 ) β

Z FD=e +e +e

There are 9 two-particle states for the Maxwell-Boltzmann case, 6 for the boson case and
only 3 for the fermion case. The 3 states in the fermion case are the ones where each particle
has a different energy. If there were m possible energy levels instead of 3, then there would
be:

n FD= (m2 )= 12 m − 12 m 2

possible fermion states.

The number of boson two-particle state would include all the possible fermion plus the m
sates where both particles have the same energy, so:

1 1
n BE=n FD +m= m 2 + m.
2 2

The number of classical two-particle states is nclass = m2. To compare the fermion or boson
cases, note that in the limit that kBT >>i for all the energies, the Boltzmann factors all go to 1
so the partition function Z just counts the number states. Thus the effective number of states
in Maxwell-Boltzmann statistics is:

1 1
n MB=Z MB ( k B T ≫ ε j )= n class= m 2 .
2! 2

Thus, we see that for 2 particles when the number of thermally accessible energies m is large,
the number of two-particle states is the same in all three cases.

For N particles and m energy levels, the same analysis applies. The difference between the
fermion and boson cases is due to the importance of states where more than one particle
occupies the same energy level. The number of such states is always down by at least a factor
of m from the number of states where all the particles have different energies. Thus, when m
gets very large, so that there are a large number of thermally accessible energy levels, then
the distinction between bosons and fermions starts to vanish. In other words, m >> N almost
all the microstates will have all the particles at different energies. For any set of N energies
for the N particles there would be N! classical assignments of the particles to the energy
levels, but only one quantum assignment. This explains why the N! Gibbs factor for identical
particles in the Maxwell-Boltzmann statistics is consistent with quantum statistical
mechanics.

In any microstate with a given N and E there will be some number ni of particles at level i, so
ni = N and niI = E. It is very difficult to work with either the microcanonical ensemble
(fixed N and E) or the canonical ensemble (fixed N and T) for quantum statistics.
Conveniently, the grand canonical ensemble comes to the rescue. In the grand canonical
ensemble, we sum over N and E, fixing instead  and T. The grand partition function is

Ƶ =∑ e− β ( E− Nμ )
N ,E

Since ni = N and niI = E the grand partition function can be written as
∞
−ni ( εi −μ )
Ƶ =∏ ∑ e =∏ Ƶ i
i ni =0 i

where ni is the number of particles in state i and Ƶi is the one-state grand canonical partition
function.

For a non-interacting Bose-system, there can be any number ni = 0, 1, 2, … of bosons in a

given state i. The single grand-canonical partition function for the state i with energy i is
then
∞
−nβ ( εi −μ )
Ƶ i =∑ e
n=0

This is a simple geometric series: there can be 0, 1, 2, etc. particles in the state, and so the
total amount of energy in the state is an integer multiple of i. Performing the sum:
∞
−nβ ( εi −μ ) 1
Ƶ i =∑ e = − β (ε i −μ )
n=0 1−e

Hence:

1
Ƶ =∏ Ƶ i=¿ ∏ −β ( εi −μ )
¿
i i 1−e

The product is over all the different states i, with i the energy of that state.
For non-interacting fermions, no two particles can occupy the same single-particle state. So
the grand canonical partition function is
− βn ( εi −μ ) − β ( ε i −μ )
Ƶi= ∑ e =1+e
n=0,1

Hence:
− βn ( εi −μ )
Ƶ ∏ Ƶ i =∏ e .
i i

To summarize:

 Fermi-Dirac statistics applies to particles of half-integer spin like electrons in metals

or white-dwarf stars or half-integer spin nuclei like protons or neutrons. Fermi-Dirac
statistics applies not just to elementary particles, but also to atoms that have an odd
number of fermions, such as 3He, which comprises 2 protons, 1 neutron and 2
electrons. In Fermi-Dirac statistics, no two identical particles can occupy the same
single-particle state.

 Bose-Einstein statistics applies to particles of integer spin, like photons, phonons,

vibrational modes, 4He atoms (=2 neutrons, 2 protons and 2 electron) or 95Rb atoms
(35 protons, 60 neutrons, 35 electrons). In Bose-Einstein statistics, any number of
bosons can occupy the same state.

 Maxwell-Boltzmann statistics are classical statistics for which calculations are

generally easier than with bosons or fermions. We treat the particles as all
distinguishable, then throw in a factor of 1/N! to the partition function to account for
indistinguishability.

For ideal gases (non-interacting particles) with any statistics, the grand-canonical
partition function can be written as
Ƶ =∏ Ƶ i
i

where Ƶi is the grand canonical partition function for a single state. For various
statistics we have:

1
Ƶ i =¿ − β ( εi −μ ) (Bose-Einstein)
1−e

−β (εi − μ)
Ƶ i =1+ e (Fermi-Dirac)
 −β (ε i− μ )
Ƶ i =exp [ e ] (Maxwell-Boltzmann)