M Sc (Physics) SEM-II (2021)

Subject: Statistical Physics

Unit III:
Ideal Fermi system: Weak and strong degeneracy, Fermi
function, Fermi energy, Behaviour of ideal Fermi gas at
absolute zero and below Fermi temperature, Fermionic
condensation, Free electrons in metals as fermions,
Electronic specific heat, Cluster expansion for classical
gas, Virial equations of states.
 Ideal Fermi System
𝟏
Mean occupation number for fermions < 𝒏𝒔 >=
𝑬𝒔 −𝝁
𝒆 𝒌𝑻 +𝟏
The number of fermions in the energy range between E to E+dE
𝒏 𝑬 𝒅𝑬 1 𝒈 𝑬 𝒅𝑬 𝒈 𝑬 𝒅𝑬
= 𝒏 𝑬 𝒅𝑬 = 𝒏 𝑬 𝒅𝑬 = −𝝁 𝑬
𝒈 𝑬 𝒅𝑬 E−𝝁 𝑬−𝝁
𝒆 𝒌𝑻+1 𝒆 𝒌𝑻 +1 𝒆 𝒌𝑻 𝒆 𝒌𝑻 +1
𝒈 𝑬 𝒅𝑬 𝝁
𝒏 𝑬 𝒅𝑬 = 𝑬 where, 𝒛 = 𝒆 𝒌𝑻
−𝟏
𝒛 𝒆 𝒌𝑻 +𝟏
𝒈 𝑬 𝒅𝑬 𝑓𝑜𝑟 𝑓𝑒𝑟𝑚𝑖𝑜𝑛𝑠 = 𝒈 . 𝒈 𝑬 𝒅𝑬 𝑓𝑜𝑟 𝑐𝑙𝑎𝑠𝑠𝑖𝑐𝑎𝑙 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠
where, 𝒈 = 2𝒔 + 1 is called fold degeneracy for quantum gas
s is spin quantum number, s = ½ for quantum particles with spin
𝑽 4𝝅𝑷2 𝒅𝑷
𝒈 𝑬 𝒅𝑬 𝑓𝑜𝑟 𝑐𝑙𝑎𝑠𝑠𝑖𝑐𝑎𝑙 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 = 3 ම𝒅𝒑𝒙 𝒅𝒑𝒚 𝒅𝒑𝒛 = 𝑽 3
𝒉 𝒉
𝑷2
For ideal fermions, E =
𝟐𝒎 𝟏 𝟑
𝟐 𝟐𝒎𝑬 𝟐𝒎𝒅𝑬 𝟐𝒎 𝟐 𝟏
𝟒𝝅𝑷 𝒅𝑷 𝟐 𝑬
𝒈 𝑬 𝒅𝑬 = 𝒈 𝑽 = 𝟒𝝅𝑽𝒈 = 𝟐𝝅𝑽𝒈 𝑬𝟐 𝒅𝑬
𝒉𝟑 𝒉𝟑 𝒉𝟐
 𝟑
𝟐𝒎 𝟐 𝟏 𝟑 𝟏
𝟐𝝅𝑽𝒈 𝑬𝟐 𝒅𝑬 ∞ 𝟐 ∞
𝒉𝟐 𝟐𝒎 𝑬𝟐 𝒅𝑬
𝒏 𝑬 𝒅𝑬 = 𝑵 = න 𝒏 𝑬 𝒅𝑬 = 𝟐𝝅𝑽𝒈 න 𝑬
𝑬 𝟎 𝒉𝟐 𝟎 −𝟏
−𝟏
𝒛 𝒆 𝒌𝑻 +𝟏 𝒛 𝒆 𝒌𝑻 +𝟏
1 1
∞ ∞
𝑬 𝑬2 𝒅𝑬 𝒌𝑻𝒙 2 𝒌𝑻𝒅𝒙
Let =𝒙 න 𝑬 =න
𝒌𝑻
0 −1 0 𝒛−1 𝒆 𝒙 + 1
𝒛 𝒆 𝒌𝑻 +1
3 1
∞
2𝒎𝒌𝑻 2 𝒙2 𝒅𝒙
𝑵 = 2𝝅𝑽𝒈 න
𝒉2 0 𝒛−1 𝒆 𝒙 + 1

𝟏 𝒛𝒆−𝒙 −𝒙 𝟏 + 𝒛𝒆−𝒙 −𝟏
= = 𝒛𝒆 = 𝒛𝒆−𝒙 (𝟏 − 𝒛𝒆−𝒙 + 𝒛𝟐 𝒆−𝟐𝒙 − 𝒛𝟑 𝒆−𝟑𝒙 + ⋯ . )
𝒛−𝟏 𝒆 𝒙 + 𝟏 𝟏 + 𝒛𝒆−𝒙
∞
𝟏 −𝒙 − 𝒛𝟐 𝒆−𝟐𝒙 + 𝒛𝟑 𝒆−𝟑𝒙 − ⋯ . = ෍ −𝟏 𝒍−𝟏 𝒛𝒍 𝒆−𝒍𝒙
= 𝒛𝒆
𝒛−𝟏 𝒆 𝒙 − 𝟏
𝒍=𝟏
𝟑 𝟑 ∞
∞ ∞ 𝟐𝒎𝒌𝑻 𝟐 ∞ 𝟑
𝟐𝒎𝒌𝑻 𝟐 𝟏 𝒍−𝟏 𝒍 −𝒍𝒙 𝟐−𝟏
𝑵 = 𝟐𝝅𝑽𝒈 න ෍ −𝟏 𝒍−𝟏 𝒍 −𝒍𝒙
𝒛𝒆 𝒙𝟐 𝒅𝒙 = 𝟐𝝅𝑽𝒈 ෍ −𝟏 𝒛 න 𝒆 𝒙 𝒅𝒙
𝒉𝟐 𝟎
𝒉𝟐 𝟎
𝒍=𝟏 𝒍=𝟏
3 ∞ 3 ∞

2𝒎𝒌𝑻 2 𝜞 2 𝜞 𝒏 = න 𝒆−𝒙 𝒙𝒏−𝟏 𝒅𝒙

𝑵 = 2𝝅𝑽𝒈 ෍ −𝟏 𝒍−𝟏 𝒛𝒍 3 𝟎 3 1
𝒉2 𝜞 = 𝝅
𝒍=1 𝒍2 𝜞 𝒏 ∞ 2 2
𝒏
= න 𝒆−𝒍𝒙 𝒙𝒏−𝟏 𝒅𝒙
𝒍 𝟎
 𝟑 ∞ 𝟏 𝟑 ∞
𝟐𝒎𝒌𝑻 𝟐
𝒍−𝟏 𝒍 𝟐 𝝅 𝟐𝝅𝒎𝒌𝑻 𝟐 −𝟏 𝒍−𝟏 𝒍
𝒛
𝑵 = 𝟐𝝅𝑽𝒈 ෍ −𝟏 𝒛 𝟑 𝑵 = 𝑽𝒈 ෍
𝒉𝟐 𝒉𝟐 𝟑
𝒍=𝟏 𝒍𝟐 𝒍=𝟏 𝒍𝟐
𝟑 ∞
𝒍−𝟏 𝒍
𝟐𝝅𝒎𝒌𝑻 𝟐 −𝟏 𝒛 𝒛𝟐 𝒛𝟑
𝑵 = 𝑽𝒈 𝒇𝟑 (𝒛) ෍ 𝟑 = 𝒛− 𝟑 + 𝟑 − ⋯ = 𝒇𝟑 (𝒛)
𝒉𝟐 𝟐 𝒍=𝟏 𝒍𝟐 𝟐𝟐 𝟑𝟐 𝟐

In the similar way for total U 3 3 𝑵 = ෍ 𝒏𝒊

∞ ∞
2𝒎 2 𝑬2 𝒅𝑬 𝒊
𝑼=න 𝒏 𝑬 𝒅𝑬 𝑬 = 2𝝅𝑽𝒈 න 𝑬
0 𝒉2 0 −1
𝒛 𝒆 𝒌𝑻 +1 𝑼 = ෍ 𝒏𝒊 𝑬𝒊
𝟑 𝟑 𝒊
∞ ∞
Let
𝑬
=𝒙 𝑬𝟐 𝒅𝑬 𝒌𝑻𝒙 𝟐 𝒌𝑻𝒅𝒙
𝒌𝑻 න 𝑬 =න
𝟎 −𝟏 𝟎 𝒛−𝟏 𝒆 𝒙 + 𝟏
𝒛 𝒆 𝒌𝑻 +𝟏
𝟑 𝟑
∞
𝟐𝒎𝒌𝑻 𝟐 𝒙𝟐 𝒅𝒙
𝑼 = 𝟐𝝅𝑽𝒈𝒌𝑻 න
𝒉𝟐 𝟎 𝒛−𝟏 𝒆 𝒙 + 𝟏
3
∞ ∞
2𝒎𝒌𝑻 2 3
𝒍−𝟏 𝒛𝒍 𝒆−𝒍𝒙 𝒙2 𝒅𝒙
U = 2𝝅𝑽𝒈𝒌𝑻 න ෍ −𝟏
𝒉2 0 𝒍=1
 𝟑 ∞
∞
𝟐𝒎𝒌𝑻 𝟐
𝒍−𝟏 𝒍
𝟓
−𝒍𝒙 𝟐−𝟏
𝑼 = 𝟐𝝅𝑽𝒈𝒌𝑻 ෍ −𝟏 𝒛 න 𝒆 𝒙 𝒅𝒙
𝒉𝟐 𝟎
𝒍=𝟏
𝟑 ∞ 𝟓
𝟐𝒎𝒌𝑻 𝟐 𝜞 𝟐
𝑼 = 𝟐𝝅𝑽𝒈𝒌𝑻 ෍ −𝟏 𝒍−𝟏 𝒛𝒍 𝟓
𝒉𝟐
𝒍=𝟏 𝒍𝟐
5 31
𝜞 = 𝝅
2 22
𝟑 ∞ 𝟑 𝟑 ∞
𝒍−𝟏 𝒛𝒍
𝟒 𝝅 𝟑 𝟐𝝅𝒎𝒌𝑻 −𝟏
𝟐
𝟐𝒎𝒌𝑻 𝟐
𝒍−𝟏 𝒛𝒍 = 𝒌𝑻𝑽𝒈 ෍
𝑼 = 𝟐𝝅𝑽𝒈𝒌𝑻 ෍ −𝟏 𝟐 𝒉𝟐 𝟓
𝒉𝟐 𝟓
𝒍=𝟏 𝒍𝟐
𝒍=𝟏 𝒍𝟐

𝟑 ∞
−𝟏 𝒍−𝟏 𝒛𝒍 𝒛𝟐 𝒛𝟑
𝟑 𝟐𝝅𝒎𝒌𝑻 𝟐
෍ = 𝒛− + − ⋯ = 𝒇𝟓 (𝒛)
𝑼= 𝒌𝑻𝑽𝒈 𝒇𝟓 (𝒛) 𝟓 𝟓 𝟓
𝟐 𝒉𝟐 𝟐 𝒍=𝟏 𝒍𝟐 𝟐𝟐 𝟑𝟐 𝟐
Behaviour of ideal Fermi system
1. Non-degenerate Fermi gas
Ideal Fermi gas at constant density behave as an ideal classical gas at
very high temperature (T → ∞) and the gas is said to be non-degenerate
gas.
𝟑ൗ 𝟑ൗ
Boltzmann limit <𝑵> 𝒉 𝟐 𝟐 𝑽 𝟐𝝅𝒎𝒌𝑻 𝟐
≪𝟏 or ≫𝟏
for Fermions 𝑽 𝟐𝝅𝒎𝒌𝑻
<𝑵> 𝒉𝟐
−µ µ
𝒆 𝒌𝑻 ≫𝟏 or 𝒆 𝒌𝑻 ≪𝟏 or z <<1
When z <<1
𝒛𝟐 𝒛𝟑 𝒛𝟐 𝒛𝟑
𝒇𝟑 𝒛 = 𝒛 − 𝟑 + 𝟑 −⋯=𝒛 and 𝒇𝟓 𝒛 = 𝒛 − 𝟓
+ 𝟓
−⋯=𝒛
𝟐 𝟐 𝟐𝟐 𝟑𝟐
𝟐𝟐 𝟑𝟐
𝟑 𝟑
𝟐𝝅𝒎𝒌𝑻 𝟐 𝟑 𝟐𝝅𝒎𝒌𝑻 𝟐
𝑵 = 𝑽𝒈 𝒛 𝑼= 𝒌𝑻𝑽𝒈 𝒛
𝒉𝟐 𝟐 𝒉𝟐
𝟑 𝟑
𝑼= 𝑵𝒌𝑻 and 𝑪𝑽 = 𝑵𝒌
𝟐 𝟐
This shows that ideal Fermi gas at constant density behave as an ideal
classical gas at very high temperature (T → ∞) and the gas is said to be
non-degenerate gas.
2. Weak degenerate Fermi gas
If the temperature is reduced such that z is less than 1 but not very less
than 1 (z < 1), under this case Fermi gas is said to be weak degenerate
Fermi gas.
Under this weak degenerate case,

𝒛𝟐 𝒛 𝒛𝟐 𝒛
𝒇𝟑 𝒛 = 𝒛 − = 𝒛(𝟏 − 𝒇𝟓 𝒛 = 𝒛 − = 𝒛(𝟏 − )
𝟑 𝟑) 𝟐
𝟓 𝟓
𝟐 𝟐𝟐 𝟐𝟐 𝟐𝟐 𝟐𝟐
𝟑 𝟑
𝟐𝝅𝒎𝒌𝑻 𝟐 𝒛 𝟐𝝅𝒎𝒌𝑻 𝟐 𝑵
𝑵 = 𝑽𝒈 𝒛(𝟏 − 𝟑)
𝑽𝒈 = 𝒛
𝒉𝟐 𝒉𝟐 𝒛(𝟏 −
𝟐𝟐 𝟑)
𝒛 𝟐𝟐
𝟑 𝒛(𝟏 − 𝟓)
𝟑 𝟐𝝅𝒎𝒌𝑻 𝟐 𝒛 𝟑 𝟐𝟐
𝑼= 𝒌𝑻𝑽𝒈 𝒛(𝟏 − ) 𝑼= 𝑵𝒌𝑻 𝒛
𝟐 𝒉𝟐 𝟓 𝟐 𝒛(𝟏 − 𝟑 )
𝟐𝟐
𝟐𝟐
𝟑 𝒛 𝒛 −𝟏
𝑼= 𝑵𝒌𝑻 (𝟏 − 𝟓) 𝟏− 𝟑
𝟑
= 𝟐 𝑵𝒌𝑻 (𝟏 −
𝒛
)(𝟏 +
𝒛
)
𝟑
= 𝟐 𝑵𝒌𝑻 (𝟏 +
𝒛
)
𝟐 𝟓 𝟑 𝟓
𝟐𝟐 𝟐𝟐
𝟐𝟐 𝟐𝟐 𝟐𝟐
 𝒇3 𝒛
2 𝒇𝟑 (𝒛)
𝒛 𝟑
1− 3 𝑼 = 𝑵𝒌𝑻 𝟏 + 𝟐
𝟐 𝟓 𝒛
3 22
𝑼 = 𝑵𝒌𝑻 1 + 𝟐𝟐 𝟏− 𝟑
2 5
22 𝟐𝟐
𝒇𝟑 (𝒛) 𝒇𝟑 (𝒛)
𝒇𝟑 (𝒛) 𝟑 𝟐 𝟐
𝟑 𝟐 𝒛 𝑼 = 𝑵𝒌𝑻 𝟏 + 𝟏+
𝑼 = 𝑵𝒌𝑻 𝟏 + 𝟓
𝟏+ 𝟑 𝟐 𝟓 𝟑 𝒛
𝟐 𝟐𝟐 𝟐𝟐 𝟏− 𝟑
𝟐𝟐 𝟐𝟐
𝟐𝟐
𝟐
𝒇𝟑 𝒛 𝒇𝟑 (𝒛) 𝒇𝟑 𝒛
𝟑 𝟐 𝟐 𝒛 𝟑 𝟐
𝑼 = 𝑵𝒌𝑻 𝟏 + + 𝟏+ 𝑼 = 𝑵𝒌𝑻 𝟏 + 𝟓
+⋯
𝟐 𝟓 𝟓 𝟑 𝟑 𝟐
𝟐𝟐 𝟐𝟐 𝟐𝟐 𝟐𝟐 𝟐𝟐
𝟑 𝟑ൗ
𝟐𝝅𝒎𝒌𝑻 𝟐 𝟑 𝑵 𝒉𝟐 𝟐
Since, 𝑵 = 𝑽𝒈 𝒇𝟑 (𝒛) 𝑼= 𝑵𝒌𝑻 𝟏 + 𝟓
+⋯
𝒉𝟐 𝟐 𝟐𝝅𝒎𝒌𝑻
𝟐 𝟐𝟐 𝑽𝒈
𝟑ൗ 𝟑
𝟑 𝑵 𝒉𝟐 𝟐
𝑵𝒌𝑻 𝑼=
𝑪𝑽 = 𝑵𝒌 𝟏 − 𝟕 + ⋯ At T → ∞ 𝟐
𝟐 𝟐𝝅𝒎𝒌𝑻
𝟑
𝟐𝟐 𝑽𝒈
𝑪𝑽 = 𝑵𝒌
𝟐
This shows that total energy of ideal Fermi gas is greater but specific heat
at constant volume is lesser than that of an ideal classical gas at high
temperature ( 0 < T < ∞) and the gas is said to be weak degenerate gas.
3. Strong degenerate Fermi gas
If the temperature is zero (T = 0), z is equal 1, under this case Fermi gas
is said to be strong degenerate Fermi gas.
𝟏
The mean occupation number for < 𝒏𝒔 >= 𝑬𝒔 −𝝁
fermions
𝒆 𝒌𝑻 +𝟏
The quantum distribution function for fermions is Fermi function
defined by the number of fermions per quantum states, f(E). Fermi
function describes the probability of occupation of quantum states.
𝒏 𝑬 𝒅𝑬 1
= f(E) =
𝒈 𝑬 𝒅𝑬 E−𝝁
𝒆 𝒌𝑻 +1
Fermi function at T = 0
1 1
When E < µ, f(E) = = =1 100% occupied
E−𝝁 𝒆 −∞ + 1
𝒆 𝒌𝑻 +1
1 1
When E > µ, f(E) = = =0 100% unoccupied
E−𝝁 𝒆∞ + 1
𝒆 𝒌𝑻 +1
1 1 1
When E = µ, f(E) = = = 50% occupied
E−𝝁 𝒆0 + 1 2
𝒆 𝒌𝑻 +1
Fermi Energy:
At T = 0, the chemical potential which is the function of temperature, µ
= µ(T) = µ(0) = EF
The chemical potential at T = 0, is said to be Fermi energy which can
be defined as the top most occupied energy level at absolute zero
temperature.
Expression for Fermi Energy at T = 0
𝟑 𝟏
∞ ∞ ∞
𝒈 𝑬 𝒅𝑬 𝟐𝒎 𝟐 𝑬𝟐 𝒅𝑬
𝑵 = න 𝒏 𝑬 𝒅𝑬 = න = 𝟐𝝅𝑽𝒈 න
𝟎 𝟎
𝑬−𝝁 𝒉𝟐 𝟎
𝑬−𝝁
𝒆 𝒌𝑻 +1 𝒆 𝒌𝑻 +1
By definition of f(E) 𝟑
𝟑
∞ 𝟐𝒎 𝟐 EF 𝟏 f(E) = 1,
𝟐𝒎 𝟐 𝟏
= 𝟐𝝅𝑽𝒈 න 𝒇(𝑬)𝑬𝟐 𝒅𝑬 = 𝟐𝝅𝑽𝒈 න 𝑬𝟐 𝒅𝑬 when E<EF
𝒉𝟐 𝒉𝟐 𝟎
𝟎 𝟐ൗ
𝟒𝝅𝑽𝒈 𝟑 𝟑ൗ 𝟑𝒉𝟑 𝑵 𝟑
𝑵= 𝟐𝒎 𝟐𝑬 𝟐 𝑬𝑭 = 𝟑
𝟑𝒉𝟑 𝑭
𝟒𝝅𝑽𝒈 𝟐𝒎 𝟐
𝟐ൗ 𝟐ൗ Fermi energy at T = 0, depends on
𝒉𝟐 𝟑𝑵 𝟑 𝒉𝟐𝟑𝝆 𝟑
𝑬𝑭 = = density of Fermi gas and mass of
𝟐𝒎 𝟒𝝅𝑽𝒈 𝟐𝒎 𝟒𝝅𝒈 each particle
Fermi temperature TF at which chemical potential reduces to zero and
𝑬
Fermi gas changes from weak degenerate to strong degenerate. 𝑻𝑭 = 𝒌𝑭
At T = 0, all energy levels At T = 0, f(E) is 1 up to E = EF then
are completely filled up f(E) = 0 at E = EF. If the
each by 1 fermion as per temperature is increased (T > 0)
Pauli’s exclusive principle then fermions just below EF gets
up to E = EF excited and move to higher
energy state just above EF
Mean energy of ideal Fermi gas at T = 0:
At T = 0, the total energy U per total number of fermions N in ideal Fermi
gas is said to be its mean energy.

Total energy of ideal Fermi gas, U 3 3

∞ ∞
2𝒎 2 𝑬2 𝒅𝑬
𝑼=න 𝒏 𝑬 𝒅𝑬 𝑬 = 2𝝅𝑽𝒈 න
0 𝒉2 0
𝑬−𝝁
𝒆 𝒌𝑻 +1
By definition of f(E) 3
∞
2𝒎 2 3
𝑼 = 2𝝅𝑽𝒈 න 𝒇(𝑬)𝑬2 𝒅𝑬
𝒉2 0
3
2𝒎 2 EF 3 f(E) = 1,
𝑼 = 2𝝅𝑽𝒈 න 𝑬2 𝒅𝑬 when E<EF
𝒉2 0

𝟒𝝅𝑽𝒈 𝟑 𝟓ൗ 𝟑 𝟒𝝅𝑽𝒈 𝟑 𝟓ൗ 𝟑 𝟒𝝅𝑽𝒈 𝟑 𝟓ൗ

𝑼= 𝟐𝒎 𝟐𝑬 𝟐 = 𝟑 𝟐𝒎 𝟐 𝑬𝑭 𝟐 = { 𝟑 𝟐𝒎 𝟐 }𝑬𝑭 𝟐
𝟓𝒉𝟑 𝑭 𝟓 𝟑𝒉 𝟓 𝟑𝒉
𝟑 𝑵 𝟓ൗ𝟐 𝟑 Mean energy, 𝑼 𝟑
𝑼= 𝑬 𝑼 = 𝑵𝑬𝑭 = 𝑬
𝟓 𝟑ൗ𝟐 𝑭 𝟓 𝑵 𝟓 𝑭
𝑬𝑭
Thus, at T = 0, 𝟐
𝟐ൗ
𝟑
𝒉 𝟑𝑵 𝟑
𝑬𝑭 = 𝑼= 𝑵𝑬𝑭 𝑪𝑽 = 𝟎
𝟐𝒎 𝟒𝝅𝑽𝒈 𝟓
 Behaviour of ideal Fermi system at T ≤ TF
Fermi used Sommerfield Lemma function to understand behaviour of
ideal Fermi system at T ≤ TF
3 1 3
∞ ∞
2𝒎 2 𝑬2 𝒅𝑬 2𝒎 2
𝑵 = න 𝒏 𝑬 𝒅𝑬 = 2𝝅𝑽𝒈 න 𝑵 = 2𝝅𝑽𝒈 𝑭3 𝒛
0 𝒉2 0
𝑬−𝝁 𝒉2 2
𝒆 𝒌𝑻 +1
3
3 3
∞ ∞ 2𝒎 2
2𝒎 2 𝑬2 𝒅𝑬 𝑼 = 2𝝅𝑽𝒈 𝑭5 𝒛
𝑼 = න 𝒏 𝑬 𝒅𝑬 . 𝑬 = 2𝝅𝑽𝒈 න 𝒉2
0 𝒉2 0
𝑬−𝝁 2
𝒆 𝒌𝑻 +1
∞
𝑬𝒏−1 𝒅𝑬
Sommerfield Lemma function, 𝑭𝒏 𝒛 = න
𝑬−𝝁
0
𝒆 𝒌𝑻 +1
2 4
𝝁𝒏 𝝅2 𝒌𝑻 7𝝅4 𝒌𝑻
𝑭𝒏 𝒛 = 1+ 𝒏 𝒏−1 + 𝒏 𝒏−1 𝒏−2 𝒏−3 +⋯
𝒏 6 𝝁 360 𝝁
3 3 2
𝝁2 𝝅2
3 1 𝒌𝑻
2 2𝝁2 𝝅2 𝒌𝑻
𝑭3 𝒛 = 1+ +. . 𝑭3 𝒛 = 1+ +⋯
3 6 2 2 𝝁 2 3 8 𝝁
2
25 5 2
𝝁2 𝝅2 5 3 𝒌𝑻
2 2𝝁2 5𝝅2 𝒌𝑻
𝑭5 𝒛 = 1+ +⋯ 𝑭5 𝒛 = 1+ +⋯
2 5 6 2 2 𝝁 2 5 8 𝝁
2
 𝟑 𝟑 𝟑
𝟐 𝟐 𝟐
𝟐𝒎 𝟐 𝟐𝝁𝟐 𝝅 𝒌𝑻 𝟒𝝅𝑽𝒈 𝟐𝒎 𝟐 𝟑 𝝅𝟐 𝒌𝑻
𝑵 = 𝟐𝝅𝑽𝒈 𝟏+ +⋯ = 𝝁𝟐 𝟏+ +⋯
𝒉𝟐 𝟑 𝟖 𝝁 𝟑 𝒉𝟐 𝟖 𝝁
3 𝟑
2 2
Since,
3 3𝑵 𝒉 4𝝅𝑽𝒈 𝟐𝒎 𝟐 𝑵
𝑬𝑭 2 = = 3
4𝝅𝑽𝒈 2𝒎 3 𝒉𝟐
𝑬𝑭 2
𝟐 −𝟏
𝟐
𝟑 𝝅𝟐 𝒌𝑻
𝟐
𝟑
𝟑 𝟑 𝝅 𝒌𝑻
𝝁𝟐 𝟏+ +⋯ = 𝑬𝑭 𝟐 𝝁𝟐 = 𝑬𝑭 𝟐 𝟏+ +⋯
𝟖 𝝁 𝟖 𝝁
𝟐
𝟐
𝝅 𝒌𝑻
𝟐 𝝅𝟐 𝒌𝑻
𝝁 = 𝑬𝑭 𝟏 − −⋯ 𝝁 = 𝑬𝑭 𝟏− −⋯
𝟏𝟐 𝝁 𝟏𝟐 𝒌𝑻𝑭

𝟐
𝝅𝟐 𝑻
𝝁 = 𝑬𝑭 𝟏− −⋯
𝟏𝟐 𝑻𝑭

𝟐
𝝁 𝝅𝟐 𝑻
= 𝟏− −⋯
𝑬𝑭 𝟏𝟐 𝑻𝑭
 𝟑 𝟑 𝟓
𝟐𝒎 𝟐 𝟐
𝑼 = 𝟐𝝅𝑽𝒈 𝑭𝟓 𝒛 𝟐𝒎 𝟐 𝟐𝝁𝟐 𝟓𝝅𝟐 𝒌𝑻
𝒉𝟐 𝑼 = 𝟐𝝅𝑽𝒈 𝟏+ +⋯
𝟐 𝒉𝟐 𝟓 𝟖 𝝁
𝟑
𝟐
𝟒𝝅𝑽𝒈 𝟐𝒎 𝟐 𝟓 𝟓𝝅𝟐 𝒌𝑻
𝑼= 𝝁𝟐 𝟏+ +⋯ 𝟑
𝟓 𝒉𝟐 𝟖 𝝁𝟓 4𝝅𝑽𝒈 𝟐𝒎 𝟐 𝑵
𝟐 𝟐 𝟐 = 3
𝟑𝑵 𝟓 𝝅𝟐 𝑻 𝟓𝝅𝟐 𝑻 3 𝒉𝟐
𝑬𝑭 2
𝑼= 𝟑 𝑬𝑭 𝟐 𝟏− −⋯ 𝟏+ +⋯
𝟏𝟐 𝑻𝑭 𝟖 𝑻𝑭
𝟓𝑬𝑭 𝟐
𝟐 𝟐 𝟐
𝟑 𝟓𝝅𝟐 𝑻 𝟓𝝅𝟐 𝑻 𝟑 𝟓𝝅𝟐 𝑻
𝑼 = 𝑵𝑬𝑭 𝟏 − + −⋯ 𝑼 = 𝑵𝑬𝑭 𝟏 + +⋯
𝟓 𝟐𝟒 𝑻𝑭 𝟖 𝑻𝑭 𝟓 𝟏𝟐 𝑻𝑭

3 5𝝅2 1 𝑵𝑬𝑭 𝝅2 1 𝑵𝒌𝑻𝑭 𝝅𝟐 𝟏

𝑪𝑽 = 𝑵𝑬𝑭 2𝑻 + ⋯ 𝑪𝑽 = 𝑻+⋯ 𝑪𝑽 = 𝑻+⋯
5 12 𝑻2𝑭 2 𝑻2𝑭 𝟐 𝑻𝟐𝑭

𝑵𝒌𝝅𝟐 𝑻
𝑪𝑽 = +⋯
𝟐 𝑻𝑭

𝑪𝑽 = 𝑨𝑻 + 𝑩𝑻3 + ⋯
When T<< 𝑻𝑭
𝑪𝑽 = 𝑨𝑻
Variation of U and CV with T for ideal Fermi and ideal Bose gases
in comparison with ideal classical gas
Free electrons in metals as fermions and electronic specific heat
In metals, atoms are periodically arranged and the electrons in the
outermost shells of atoms are free to move in the volume of metal. These
free electrons form an electron gas in metal.
ђ
Electrons have spin 𝟐 and wavefunction antisymmetric therefore,
electrons follow Pauli’s exclusive principle and they are fermions and
obey FD statistics. Fermi energy of electrons at T = 0 in metals according
to FD statistics; 𝟐ൗ 𝟐ൗ
𝒉 𝟐 𝟑𝑵 𝟑 𝒉 𝟐 𝟑𝝆 𝟑
𝑬𝑭 = =
𝟐𝒎 𝟒𝝅𝑽𝒈 𝟐𝒎 𝟒𝝅𝒈
For electrons, the fold degeneracy 𝒈 = 2𝒔 + 1 = 2
𝟐ൗ
𝒉𝟐 𝟑𝝆 𝟑
𝑬𝑭 =
𝟐𝒎 𝟖𝝅
For the metals with high density of electrons, Fermi temperature is of the
order of 104-105. Thus, the free electron gas in metals is highly
degenerate at room temperature.
The total energy of free electron gas in metals at T = 0,
𝟐ൗ
𝟑 𝟑 𝒉𝟐 𝟑𝝆 𝟑
𝑼 = 𝑵𝑬𝑭 𝑼= 𝑵
𝟓 𝟓 𝟐𝒎 𝟖𝝅
The pressure of free electron gas in metals at T = 0,
𝟐ൗ 𝟐ൗ
𝟐𝑼 𝟐 𝟑 𝒉 𝟑𝝆 𝟐 𝟑 𝟐 𝟐
𝒉 𝟑𝝆 𝟑
𝑷= 𝑷= 𝑵 𝑷= 𝑵
𝟑𝑽 𝟑𝑽 𝟓 𝟐𝒎 𝟖𝝅 𝟓𝑽 𝟐𝒎 𝟖𝝅
This pressure of free electron gas in metals at T = 0, is usually much
higher than that of the usual gas and tends to expand the metal which is
counter balanced by the attractive forces between the atoms within the
metal. Thus, the free electrons are usually prevented from leaving the
metal under this high pressure. However, at a very high temperature,
some of the electrons may have sufficient energy to escape from the
metal.
From the behaviour of ideal Fermi system at T ≤ TF

𝟐
𝟑 𝟓𝝅𝟐 𝑻 𝑵𝒌𝝅𝟐 𝑻
𝑼 = 𝑵𝑬𝑭 𝟏 + +⋯ 𝑪𝑽 = +⋯
𝟓 𝟏𝟐 𝑻𝑭 𝟐 𝑻𝑭
𝟑
At T = 0, 𝑼 = 𝑵𝑬𝑭 𝑪𝑽 = 𝟎
𝟓
When we consider 𝑪𝑽 of metal, it is the sum of the contribution of the
free electrons and the lattice vibration.
Thus, at low temperature, 𝑪𝑽 = 𝑪𝑽 𝒆 + 𝑪𝑽 𝒍

According to Debye theory at low temperature,

𝟑
𝟏𝟐𝑵𝒌𝝅𝟒 𝑻
𝑪𝑽 𝒍 =
𝟓 𝑻𝑫
Where, 𝑻𝑫 is Debye temperature of metal which is around 100 to 400 K
𝟑
Thus, at low temperature, 𝑵𝒌𝝅𝟐 𝑻 𝟏𝟐𝑵𝒌𝝅𝟒 𝑻
𝑪𝑽 = +
𝟐 𝑻𝑭 𝟓 𝑻𝑫
𝑵𝒌𝝅𝟐 𝟏𝟐𝑵𝒌𝝅𝟒 𝟑 𝑪𝑽
𝑪𝑽 = 𝑻+ 𝟑
𝑻 𝑪𝑽 = 𝑨𝑻 + 𝑩𝑻𝟑 = 𝑨 + 𝑩𝑻𝟐
𝟐𝑻𝑭 𝟓𝑻𝑭 𝑻

𝑵𝒌𝝅𝟐 𝟏𝟐𝑵𝒌𝝅𝟒
𝑨= 𝑩=
𝟐𝑻𝑭 𝟓𝑻𝑫 𝟑

Experimentally, A and B determined from

graph and Fermi temperature and Debye
temperature can be determined. By knowing
Fermi temperature, electronic specific heat
is determined.
 Fermionic condensation
Fermionic condensate is a superfluid phase formed by fermionic particles at
low temperatures. It is closely related to the Bose–Einstein condensate, a
superfluid phase formed by bosonic particles under similar conditions. The
earliest recognized fermionic condensate described the state of electrons in
a superconductor. The first atomic potassium (K40) fermionic condensate
was created by Deborah Jin and team in 2003. But it was not sixth state of
matter. At very low temperature, fermionic atoms changes its spin to that of
bosonic spin when form their cooper pairs and hence it is nothing but Bose-
Einstein condensate.
BCS theory of superconductor (1957)
 Cluster expansion for classical real gas
Equation of state for ideal gas 𝑷𝑽 = 𝑵𝒌𝑻
𝒂
Vander wall's equation of state for real gas 𝑷+ + 𝑽 − 𝒃 = 𝑵𝒌𝑻
𝑽2
Virial equation of state for real gas
𝑷
= ෍ 𝑩𝒍 (𝑻)𝝆𝒍 = 𝑩𝟏 𝝆𝟏 + 𝑩𝟐 𝝆𝟐 + 𝑩𝟑 𝝆𝟑 + ⋯
𝒌𝑻
𝒍=𝟏
Where, 𝑩𝒍 (𝑻) are Virial Coefficients and ρ be density of classical real gas.

We know, Canonical partition function for classical ideal gas

𝟏 𝑬
− 𝒏
𝑸𝑵 = ෍ 𝒆 𝒌𝑻
𝑵! 𝒉𝟑𝑵
𝒏

𝟏 −
𝑬(𝒒,𝒑)
𝑸𝑵 = 𝟑𝑵 න 𝒆 𝒌𝑻 𝒅𝒒𝒅𝒑
𝑵! 𝒉
But, Canonical partition function for classical real gas
𝟏 −
𝑯(𝒒,𝒑)
𝑸𝑵 = න 𝒆 𝒌𝑻 𝒅𝒒𝒅𝒑
𝑵! 𝒉𝟑𝑵
 𝟑𝑵
𝟏 𝒑𝟐𝒊 𝑼(𝒓𝟏 ,…𝒓𝑵
− σ𝟑𝑵
𝒊=𝟏𝟐𝒎𝒌𝑻+
𝑸𝑵 = න 𝒆 𝒌𝑻 𝒅𝒓𝟏 𝒅𝒓𝟐 . . ෑ 𝒅𝒑𝒊
𝑵! 𝒉𝟑𝑵
𝒊=𝟏
𝟑𝑵
𝟏 𝟑𝑵 𝒑𝟐𝒊 −
𝑼(𝒓𝟏 ,…𝒓𝑵
− σ𝒊=𝟏 𝒌𝑻
𝑸𝑵 = න 𝒆 𝟐𝒎𝒌𝑻 ෑ 𝒅𝒑𝒊 න 𝒆 𝒅𝒓𝟏 𝒅𝒓𝟐 . .
𝑵! 𝒉𝟑𝑵
𝒊=𝟏
𝟑𝑵 𝟑𝑵
𝒖𝒊𝒋 (𝒓𝒊𝒋 )
𝟐𝝅𝒎𝒌𝑻 𝟐
− σ𝒊,𝒋 𝟐𝝅𝒎𝒌𝑻/𝒉𝟐 𝟐
𝑸𝑵 = න𝒆 𝒌𝑻 𝒅𝒓𝟏 𝒅𝒓𝟐 … 𝑸𝑵 = 𝓨𝑵
𝑵! 𝒉𝟑𝑵 𝑵!
𝒖𝒊𝒋 𝒓𝒊𝒋
− σ𝒊,𝒋
Where, 𝓨𝑵 = න𝒆 𝒌𝑻 𝒅𝒓1 𝒅𝒓2 … is called configurational partition function
𝒖𝒊𝒋 𝒓𝒊𝒋
−
Mayer f-function, 𝒇𝒊𝒋 = 𝒆 𝒌𝑻 −𝟏
𝒖𝒊𝒋 𝒓𝒊𝒋 𝒖𝒊𝒋 𝒓𝒊𝒋
− −
𝒆 𝒌𝑻 = 𝟏 + 𝒇𝒊𝒋 ෑ𝒆 𝒌𝑻 = ෑ(𝟏 + 𝒇𝒊𝒋 )
𝒊≠𝒋 𝒊≠𝒋

𝒖𝒊𝒋 𝒓𝒊𝒋
− σ𝒊≠𝒋
𝒆 𝒌𝑻 = 1 + ෍ 𝒇𝒊𝒋 + ෍ 𝒇𝒊𝒋 𝒇𝒎𝒏 + ⋯
𝒊≠𝒋 𝒊≠𝒋,𝒎≠𝒏
𝒖𝒊𝒋 𝒓𝒊𝒋
− σ𝒊≠𝒋
If 𝒇𝒊𝒋 = 𝟎, 𝒆 𝒌𝑻 =1
Therefore,
𝒖𝒊𝒋 𝒓𝒊𝒋
− σ𝒊,𝒋
𝓨𝑵 = න𝒆 𝒌𝑻 𝒅𝒓1 𝒅𝒓2 … = න𝒅𝒓1 … . . 𝒅𝒓𝑵 = 𝑽𝑵
 3𝑵 3ൗ 𝑵
Τ 2
2𝝅𝒎𝒌 𝑻 𝒉 2 1 2𝝅𝒎𝒌𝑻 2
And hence, 𝑸𝑵 = 𝑽𝑵 𝑸𝑵 = 𝑽
𝑵! 𝑵! 𝒉2
This is the canonical partition function for ideal gas, if Mayer function is zero.
Configurational partition function for classical real gas
𝓨𝑵 = න 𝟏 + ෍ 𝒇𝒊𝒋 + ෍ 𝒇𝒊𝒋 𝒇𝒎𝒏 + ⋯ 𝒅𝒓𝟏 𝒅𝒓𝟐 …
𝒊≠𝒋 𝒊≠𝒋,𝒎≠𝒏
All the terms in the expansion are to associate a graph with each other. A N-
particle graph consists of N number of circles with any number of line
segments joining a pair of circles.

𝓨𝟔 = න 𝒇𝟏𝟐 𝒇𝟏𝟒 𝒇𝟐𝟓 𝒇𝟑𝟓 𝒇𝟑𝟔 𝒅𝒓𝟏 … . 𝒅𝒓𝟔

𝓨𝑵 = 𝑺𝒖𝒎 𝒐𝒇 𝒂𝒍𝒍 𝑵 − 𝑷𝒂𝒓𝒕𝒊𝒄𝒍𝒆 𝒈𝒓𝒂𝒑𝒉

We now define Cluster Integral

𝟏
𝒃𝒍 = 𝑺𝒖𝒎 𝒐𝒇 𝒂𝒍𝒍 𝒑𝒐𝒔𝒔𝒊𝒃𝒍𝒆 𝒍 − 𝒄𝒍𝒖𝒔𝒕𝒆𝒓
𝒍! 𝑽
𝟏 𝟏 𝟏
𝒃𝟏 = න 𝒅𝒓𝟏 = 𝑽 = 𝟏 𝒃𝟐 = න 𝒇𝟏𝟐 𝒅𝒓𝟏 𝒅𝒓𝟐
𝑽 𝑽 𝟐𝑽
𝟏
𝒃𝟑 = න 𝒇𝟏𝟐 𝒇𝟏𝟑 +𝒇𝟐𝟑 𝒇𝟏𝟑 + 𝒇𝟏𝟐 𝒇𝟐𝟑 +𝒇𝟏𝟐 𝒇𝟏𝟑 𝒇𝟐𝟑 𝒅𝒓𝟏 𝒅𝒓𝟐 𝒅𝒓𝟑
𝟔𝑽
And so on for other cluster integrals
If 𝑆 𝑚𝑙 be the sum of all graphs corresponding to the set of integers 𝑚𝑙
which specify the collection of graphs, then

𝓨𝑵 = ෍ 𝑺 𝒎𝒍
{𝒎𝒍 }

To determine 𝑆 𝑚𝑙 , let us consider N-particles as N circles having m1

unit clusters, m2 two particle clusters, m3 three particle clusters, … ml l-
particle clusters and so on and find all permutations of filling N circles
such that the total number of particles with l-particle clusters given by

𝑵 = 1𝒎1 + 2𝒎2 + 3𝒎3 + ⋯ = ෍ 𝒍𝒎𝒍

𝒍
The sum over all permutations for N-circles filling gives 𝑆 𝑚𝑙 as
𝑺 𝒎𝒍 = ෍ 𝟎 … 𝟎 𝟎 − 𝟎 … . 𝟎 − 𝟎 … . 𝒎𝟏 𝒎𝟏
𝟎 = 𝟏! 𝑽𝒃𝟏
𝑷
𝒎𝟐 𝒎𝟐
𝒎𝟏 𝒎𝟐 𝟎−𝟎 = 𝟐! 𝑽𝒃𝟐
𝑺 𝒎𝒍 = ෍ 𝟎 𝟎−𝟎 …
𝑷
and so on

𝑆 𝑚𝑙 is equal to the number of terms in sum over all permutation

times the value of each term in the sum
෍0 𝒎1 0−0 𝒎2 … = 𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒕𝒆𝒓𝒎𝒔 𝑽𝒂𝒍𝒖𝒆 𝒐𝒇 𝒆𝒂𝒄𝒉 𝒕𝒆𝒓𝒎
𝑷
 𝑵!
𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒕𝒆𝒓𝒎𝒔 =
ς𝒍 𝒎𝒍 ! ς𝒍 𝒍!𝒎𝒍
Actually, there must be N! terms, but some of the terms are repeated
which does not give new graph and they are

ෑ 𝒎𝒍 ! due to ml clusters among themselves does not lead to new graph

𝒍

ෑ 𝒍!𝒎𝒍 due to l-particles in l-clusters among themselves does not lead to

𝒍 new graph
𝑽𝒂𝒍𝒖𝒆 𝒐𝒇 𝒆𝒂𝒄𝒉 𝒕𝒆𝒓𝒎 = ෑ 𝒍! 𝑽𝒃𝒍 𝒎𝒍

𝒍
𝒎𝒍
𝑵! 𝑽𝒃𝒍 𝒎𝒍
𝑺 𝒎𝒍 = ෑ 𝒍! 𝑽𝒃𝒍 𝑺 𝒎𝒍 = 𝑵! ෑ
ς𝒍 𝒎𝒍 ! ς𝒍 𝒍!𝒎𝒍 𝒎𝒍 !
𝒍 𝒍
𝑽𝒃𝒍 𝒎𝒍
𝓨𝑵 = ෍ 𝑺 𝒎𝒍 = ෍ 𝑵! ෑ
𝒎𝒍 !
𝒎𝒍 𝒎𝒍 𝒍
𝟑𝑵 𝟑𝑵
𝟐𝝅𝒎𝒌𝑻 𝟐 𝟐𝝅𝒎𝒌𝑻 𝟐 𝑽𝒃𝒍 𝒎𝒍
𝑸𝑵 = 𝓨𝑵 = ෍ 𝑵! ෑ
𝑵! 𝒉𝟑𝑵 𝑵! 𝒉𝟑𝑵 𝒎𝒍 !
𝒎𝒍 𝒍

𝟏 𝑽𝒃𝒍 𝒎𝒍
𝑸𝑵 = 𝟑𝑵 ෍ ෑ
𝝀𝑻 𝒎𝒍 !
𝒎𝒍 𝒍
 Grand partition function of classical real gas,
𝝁𝑵 𝝁𝑵 𝟏 𝑽𝒃𝒍 𝒎𝒍
𝒁𝑵 = ෍ 𝒆 𝒌𝑻 𝑸𝑵 = ෍ 𝒆 𝒌𝑻 𝟑𝑵
෍ ෑ
𝝀𝑻 𝒎𝒍 !
𝑵 𝑵 𝒎𝒍 𝒍
𝝁 𝑵 𝝁 σ𝒍 𝒍𝒎𝒍
𝒆𝒌𝑻 𝑽𝒃𝒍 𝒎𝒍 𝒆𝒌𝑻 𝑽𝒃𝒍 𝒎𝒍
𝒁𝑵 = ෍ ෍ ෑ 𝒁𝑵 = ෍ ෍ ෑ
𝝀𝟑𝑻 𝒎𝒍 ! 𝝀𝟑𝑻 𝒎𝒍 !
𝑵 𝒎𝒍 𝒍 𝒎𝒍 𝒎𝒍 𝒍
𝒎𝒍 𝝁
𝑽𝒃 𝒆𝒌𝑻
𝒁𝑵 = ෍ 𝒙 σ𝒍 𝒍𝒎𝒍 ෍ ෑ
𝒍 Where, =𝒙
𝒎𝒍 ! 𝝀𝟑𝑻
𝒎𝒍 𝒎𝒍 𝒍

𝑽𝒃𝒍 𝒎𝒍 𝒎𝒍 𝑽𝒃𝒍 𝒎𝒍
𝒁𝑵 = ෍ 𝒙 𝟏𝒎𝟏 +𝟐𝒎𝟐 +⋯
෍ ෑ 𝒁𝑵 = ෍ ෑ 𝒙𝒍 ෍ ෑ
𝒎𝒍 ! 𝒎𝒍 !
𝒎𝒍 𝒎𝒍 𝒍 𝒎𝒍 𝒍 𝒎𝒍 𝒍

𝒎𝒍 𝒎𝒍
𝒙𝒍 𝑽𝒃𝒍 𝒙𝒍 𝑽𝒃𝒍
𝒁𝑵 = ෍ ෑ 𝒁𝑵 = ෑ ෍
𝒎𝒍 ! 𝒎𝒍 !
𝒎𝒍 𝒍 𝒍 𝒎𝒍

𝒍
𝒁𝑵 = ෑ 𝒆𝒙 𝑽𝒃𝒍
𝒍
Virial equations of states for real gas
𝑷
= ෍ 𝑩𝒍 (𝑻)𝝆𝒍 = 𝑩𝟏 𝝆𝟏 + 𝑩𝟐 𝝆𝟐 + 𝑩𝟑 𝝆𝟑 + ⋯
𝒌𝑻
𝒍=𝟏

Classically using grand canonical ensemble,

𝒍 𝒍
𝑵 = 𝒍𝒏𝒁𝑵 = 𝒍𝒏 ෑ 𝒆𝒙 𝑽𝒃𝒍 = ෍ 𝒍𝒏 𝒆𝒙 𝑽𝒃𝒍 = ෍ 𝒙𝒍 𝑽𝒃𝒍
𝒍 𝒍 𝒍

𝑷 𝑵 𝒍𝒏𝒁𝑵
= = = ෍ 𝒙𝒍 𝒃𝒍
𝒌𝑻 𝑽 𝑽
𝒍

𝝏Ω 𝝏𝒍𝒏𝒁𝑵 𝝏 σ𝒍 𝒙𝒍 𝑽𝒃𝒍
𝑵=− = 𝒌𝑻 = 𝒌𝑻
𝝏𝝁 𝝏𝝁 𝝏𝝁
𝝁
𝝏 σ𝒍 𝒙𝒍 𝑽𝒃𝒍 𝝏𝒙 𝝏 σ𝒍 𝒙𝒍 𝑽𝒃𝒍 𝒆𝒌𝑻 𝟏
𝑵 = 𝒌𝑻 = 𝒌𝑻
𝝏𝒙 𝝏𝝁 𝝏𝒙 𝝀𝟑𝑻 𝒌𝑻
𝑵 𝝏 σ𝒍 𝒙𝒍 𝒃𝒍
𝝆= = 𝒙 = ෍ 𝒍𝒙𝒍 𝒃𝒍
𝑽 𝝏𝒙
𝒍
 𝑷 𝑷 𝟏
= ෍ 𝑩𝒍 (𝑻)𝝆𝒍 = ෍ 𝑩𝒍 (𝑻)𝝆𝒍−𝟏
𝒌𝑻 𝒌𝑻 𝝆
𝒍=𝟏 𝒍=𝟏

σ𝒍 𝒙𝒍 𝒃𝒍
𝒍
= ෍ 𝑩𝒍 (𝑻)𝝆𝒍−𝟏 ෍ 𝒍𝒙𝒍 𝒃𝒍 ෍ 𝑩𝒍 (𝑻)𝝆𝒍−𝟏 = ෍ 𝒙𝒍 𝒃𝒍
σ𝒍 𝒍𝒙 𝒃𝒍
𝒍=𝟏 𝒍 𝒍=𝟏 𝒍

Equating the coefficient of power of x on both sides

(1) For power 1 of x 𝑩𝟏 𝑻 = 𝟏

(2) For power 2 of x 𝑩𝟐 𝑻 = −𝒃𝟐

(3) For power 3 of x 𝑩𝟑 𝑻 = 𝟒𝒃𝟐𝟐 − 𝟐𝒃𝟑

Thus, Virial expansion of equation of state for classical real gas

𝑷 𝑷
= 𝑩𝟏 𝝆𝟏 + 𝑩𝟐 𝝆𝟐 + 𝑩𝟑 𝝆𝟑 + ⋯ = 𝝆 − 𝒃𝟐 𝝆𝟐 + 𝟒𝒃𝟐𝟐 − 𝟐𝒃𝟑 𝝆𝟑 + ⋯
𝒌𝑻 𝒌𝑻
𝑷
= 𝝆 𝟏 − 𝒃𝟐 𝝆 + 𝟒𝒃𝟐𝟐 − 𝟐𝒃𝟑 𝝆𝟐 + ⋯
𝒌𝑻