The Quantum Distribution Functions

Consider an ideal gas of identical particles, N in number. Let s represent the state of a
single particle and S the state of the whole gas. Suppose that when the gas is in state S, n1
particles are in state s=1 with energy ε1, n2 particles in state s=2 with energy ε2, etc. The
total energy of the gas, therefore, is

𝐸𝑆 = ∑ 𝑛𝑠ϵ𝑠
𝑆

and the total number of particles is

𝑁 = ∑ 𝑛𝑠
𝑆

The partition function can be given by,

−β𝐸𝑠
𝑍 = ∑𝑒
𝑆

here summation is taken over all possible states S.

There are three different statistics obeyed by different kind of particles-

1. MB Statistics- In this case the particles are distinguishable. The partition function is-

−β∑𝑛𝑠ε𝑠
𝑆
𝑍 = ∑𝑒
𝑆

where the summation is over all states S,

i.e. over all possible values of ns.
The mean number of particles in state s is given by,
−β∑𝑛𝑠ϵ𝑠
∑𝑛𝑠𝑒 𝑆

𝑆
< 𝑛𝑠 > =
−β∑𝑛𝑠ϵ𝑠
𝑆
∑𝑒
𝑆

1 ∂𝑙𝑛𝑍
=− β ∂ε𝑠
............................(iv)

The partition function can as well as written as,

 −βε𝑠 −βε𝑠 ……
𝑍= ∑ 𝑒 1
𝑒 2

𝑠1,𝑠2

−βε𝑠 −βε𝑠
= [∑ 𝑒 1
][∑ 𝑒 ]….
2

𝑠1 𝑠2

𝑁
−βε𝑠
= [∑ 𝑒 ]
𝑠
Taking 𝑙𝑛 both sides we get,

−βε𝑠
𝑙𝑛𝑍 = 𝑁𝑙𝑛(∑ 𝑒 )
𝑠

Therefore, substituting this in equation (iv), we have,

−βε𝑠
𝑁𝑒
< 𝑛𝑠 > = −βε𝑠
∑𝑒
𝑠

This is the MB distribution.

2. BE- Statistics-

In this case the particles are indistinguishable. The BE- statistics can be treated
conveniently using the grand canonical ensemble.

The grand partition function is given by,

( )
−β 𝑛1ε1+𝑛2ε2+… +μβ 𝑛1+𝑛2+… ( )
𝑍 = ∑𝑒
𝑆

where the summation is over all possible states i.e. over all possible
numbers of particles in each single particle state. The number of particles ni in each state i,

will be 0,1,2..., subjected to the condition ∑ 𝑛𝑖 = 𝑁. Here µ is the chemical potential which is

related to 𝑍 as µ =− 𝑘𝑇𝑙𝑛𝑧.
Therefore, the partition function becomes,

−β(ε1−μ)𝑛1 (
−β ε2−μ 𝑛2 )
𝑍 = (∑ 𝑒 )(∑ 𝑒 ) ...
𝑛1 𝑛2
Now,

( )
−β ε1−μ 𝑛1 −β(ε1−μ) −2β(ε1−μ)
∑𝑒 ) = 1 +𝑒 +𝑒 +…
𝑛1

This is a geometric series. Hence,

(
−β ε1−μ 𝑛1 ) 1
∑𝑒 = −β(ε1−μ)
𝑛1 1−𝑒

Therefore,

𝑍= ( 1−𝑒
1
(
−β ε1−μ ) )( 1−𝑒
1
(
−β ε2−μ ) ) ...

1
=∑ −β(ε𝑠−μ)
𝑠 1−𝑒
Taking 𝑙𝑛 both sides we get,

−β ε𝑠−μ ( )
𝑙𝑛𝑍 =− ∑ 𝑙𝑛⁡(1 − 𝑒 )
𝑆

Now, we know that,

1 ∂𝑙𝑛𝑍
𝑁= β ∂μ

So,
1 ∂ −β ε𝑠−μ ( )
𝑁 =− β ∂μ
∑ 𝑙𝑛⁡[1 − 𝑒 ] = ∑< 𝑛𝑠 >
𝑠

From this expression one can infer that the sth term in the sum represents the average
number of molecules in the sth level.
Now,
1 ∂ −β ε𝑠−μ ( )
< 𝑛𝑠 > =− β ∂μ
𝑙𝑛⁡[1 − 𝑒 ]
−β ε𝑠−μ ( )
𝑒
= −β ε𝑠−μ ( )
1−𝑒

1
= (
β ε𝑠−μ )
𝑒 −1

= 𝑓(ε𝑠)
 β(ε𝑠−μ)
Since, the number of bosons in any state cannot be negative, 𝑒 must be greater than
( )
unity, i.e. ε𝑠 − μ > 1 for all ε𝑠. The lowest energy of a single particle state of a boson gas

is zero. Hence, μ for an ideal gas always be negative.

The last equation takes a simpler form in the case of photons, which have spin one and,
hence, are bosons. Photons can be considered as an ideal gas, since it follows from
electromagnetic theory that their interactions are completely negligible. Because photons
may be absorbed and re-emitted by the walls of the enclosure, the number of photons

inside the enclosure is not conserved. The condition∑ 𝑛𝑠 = 𝑁, therefore, is not imposed on
𝑠

the distribution.
∂𝑙𝑛𝑍
Hence, ∂𝑁
= 0

∂𝐸 ∂𝑙𝑛𝑍
Therefore, μ = ( ∂𝑁 ) = 𝑘𝑇 ∂𝑁
=0
𝑉,𝑇

and the distribution function takes the form,

1
< 𝑛𝑠 >= βε𝑠
𝑒 −1

In fact, this formula could have been derived directly. As µ = 0, we can write,
−βε𝑠
𝑍 = ∑𝑒
𝑠

−β(𝑛1ε1+𝑛2ε2+…)
= ∑ 𝑒
𝑛1,𝑛2,…
∞ −β𝑛1ε1 ∞ −β𝑛2ε2
= (∑ 𝑒 )(∑ 𝑒 )….
𝑛1 𝑛2

= ( 1
−βε1
1−𝑒
)( 1−𝑒
1
−βε2 ) ...

= ( 1−𝑒
1
−βε𝑠 )
Therefore,
 −βε𝑠
𝑙𝑛𝑍 =− ∑ 𝑙𝑛⁡(1 − 𝑒 )
𝑠
and

1 ∂𝑙𝑛𝑍 1
< 𝑛𝑠 >=− β ∂ε𝑠
= βε𝑠
𝑒 −1
3. FD- Statistics

In this case particles are identical and indistinguishable. Here, 𝑛𝑠 = 0 or 1.

Here, the partition function is given by,

( )
)(1 + 𝑒 ( )) ...
β μ−ε1 β μ−ε2
(
𝑍 = 1 +𝑒

(
β μ−ε𝑠 )
= ∑(1 + 𝑒 )
𝑠

Taking 𝑙𝑛 both sides, we get,

(
β μ−ε𝑠 )
𝑙𝑛𝑍 = ∑ 𝑙𝑛{1 + 𝑒 }
𝑠

Hence,

1 ∂𝑙𝑛𝑍 1 ∂ (
β μ−ε𝑠 ) β(μ−ε𝑠)
𝑒
𝑁= β ∂μ
= β ∂µ
[∑ 𝑙𝑛{1 + 𝑒 }] = ∑ β(μ−ε𝑠) = ∑< 𝑛𝑠 >
𝑠 𝑠 1+𝑒

Therefore,
1
< 𝑛𝑠 >= β(ε𝑠−μ)
𝑒 +1

This is the distribution function for FD- Statistics.

 The Boltzmann limit of BE- and FD- Statistics
The average number of particles in any energy state ε𝑠 is given by,

1
< 𝑛𝑠 >= β(ε𝑠−μ)
𝑒 ±1

where the upper sign refers to FD- statistics and the lower to BE-
statistics.

Suppose now,

−βμ β(ε𝑠−μ)
𝑒 ≫1 i.e. 𝑒 ≫1
In this case,

1 βμ −βε𝑠
< 𝑛𝑠 > ≈ β(ε𝑠−μ) =𝑒 𝑒
𝑒

Further, because ∑< 𝑛𝑠 >= 𝑁

βμ −βε𝑠
𝑒 ∑𝑒 = 𝑁
𝑠

Therefore,
βμ 𝑁
𝑒 = −βε𝑠
∑𝑒

And, hence,
−βε𝑠
𝑁𝑒
< 𝑛𝑠 > = −βε𝑠
∑𝑒

which is MB- distribution.

Thus, quantum statistics gives the Boltzmann form in the limiting case when,
−βμ
𝑒 ≫1

This variation of < 𝑛𝑠 > with β(ε − μ) in the three cases is shown in the adjoining figure