Thermodynamics of quantum gases

We now wish to study the thermodynamic properties of an ideal gas of quantum particles, in grand
canonical ensemble. For this purpose, the grand potential that we introduced earlier, come in useful.
The grand potential is defined as
Ξ = −𝑘! 𝑇 ln 𝑍 = −𝑃 𝑉
It implies

⎧− 0 ln11 − 𝜍 𝑒 "# %! 5 (Bose − Einstein )

𝑃 𝑉 ⎪ &
= ln 𝑍 =
𝑘! 𝑇 ⎨ 0 ln11 + 𝜍 𝑒 "# %! 5 (Fermi − Dirac )
⎪
⎩ &
Where the fugacity 𝜍 = 𝑒 #' . Average number of particles in the system in terms of fugacity is given
by
1
⎧0 "( #% (Bose − Einstein )
⎪ & 𝜍 𝑒 ! − 1
〈𝑁〉 =
⎨0 1
⎪ (Fermi − Dirac )
⎩ 𝜍 𝑒 ! + 1
"( #%
&

To proceed any further, we need to know the details of the system, namely the precise form of the single
particle energies 𝜖& . Let us consider the case of quantum gas in a cubical box of length L.

The corresponding Schrödinger equation (x component) is

𝜕 ) 𝜓(𝑥)
+ 𝑘 ) 𝜓(𝑥) = 0
𝜕𝑥 )
Where 𝑘 ) = 2 𝑚 𝐸 /ℏ) . For a free particle, i.e., in the absence of
interaction between the particles, the momentum of the particles is defined as 𝑝 = √2 𝑚 𝐸. This
implies, 𝑝 = ℏ 𝑘. The general solution of the

𝜓(𝑥) = 𝐴 𝑒 * & + + 𝐵 𝑒 "* & +

Where A and B are constants. The derivative of the wave function is

𝜓 , (𝑥) = 𝐴 𝑖𝑘 𝑒 * & + − 𝐵 𝑖𝑘 𝑒 "* & +

Consider the periodic boundary conditions at the channel walls, which represent a macroscopic system.
This implies
𝜓(0) = 𝜓(𝐿) ; 𝜓 , (0) = 𝜓 , (𝐿)
These boundary conditions give
𝐴 + 𝐵 = 𝐴 𝑒 * & - + 𝐵 𝑒 "* & -
𝐴 − 𝐵 = 𝐴 𝑒 * & - − 𝐵 𝑒 "* & -

If we add the above two equations, we get 1 = 𝑒 * & - . Note that 𝑒 * & - = cos(𝑘 𝐿) + 𝑖 sin(𝑘 𝐿). The
only solution for this is 𝑘 𝐿 = 2 𝑛 𝜋. Since 𝑝 = ℏ 𝑘, we get the following possible values of momentum

2 𝑛 𝜋
𝑝 = ℏ 𝑘 = ℏ
𝐿
𝑛 ℎ
𝑝. =
𝐿
This implies, 𝑛 = 𝑝. 𝐿/ℎ. As the particle is confined in a cubical box, there are three quantum numbers
𝑛+ , 𝑛/ , 𝑛0 . As the length of the box becomes very large (macroscopic), the momenta are so closely
spaced that they can be assumed to form a continuum. So, in this limit, instead of summing over
𝑛+ , 𝑛/ , 𝑛0 one can integrate over 𝑝+ , 𝑝/ , 𝑝0 . This implies,

3 3 3
𝑉
0 ⟶ ` 𝑑 𝑝 ` 𝑑 𝑝 ` 𝑑 𝑝
ℎ2 "3 + "3 / "3 0
." ,.# ,.$

Note that the actual integration is over the position and momentum coordinates in the phase space, same
as in the classical case. The contribution from the position coordinates (in 3D) is 𝑉, the physical volume
of the system.

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3
𝑉
0 ⟶ ` 4 𝜋 𝑝) 𝑑𝑝
ℎ2 4
." ,.# ,.$

For an ideal gas of bosons, the average number of particles can now be written as

4 𝜋 𝑉 3 𝑝)
〈𝑁〉 = ` 𝑑𝑝
ℎ2 4 𝜍 "( 𝑒#5% /()8) − 1
Choosing a new variable 𝑡 = 𝛽𝑝) /(2𝑚), we get

3
2 𝑉 2/) √𝑡
〈𝑁〉 = (2𝜋 𝑚 𝑘! 𝑇) ` 𝑑𝑡
√𝜋 ℎ2 4 𝜍 𝑒 : − 1
"(
Where 𝜆 = ℎ/f2𝜋 𝑚 𝑘! 𝑇 and the integral is defined as
3
1 𝑡 ;"(
𝑔; (𝜍) = ` "( : 𝑑𝑡
Γ(𝜈) 4 𝜍 𝑒 − 1
Here, Γ(𝜈) is the gamma function. Thus, number of particles per unit volume can be written as

〈𝑁〉 1
= 2 𝑔2/) (𝜍)
𝑉 𝜆
In the process of approximating the summation over the quantum state by integral over momenta, have
inadvertently assigned weight zero to the lowest (𝑝 = 0) term. This is clearly wrong, and we would
<
like to separate out the zero-energy contribution from the sum. That term is simply 〈𝑛4 〉 = ("< , which

is obtained by putting 𝑘 = 0 and 𝜖& = 0 in

1
〈𝑛& 〉 =
𝜍 "( 𝑒#%! −1
Thus, the correct expression for the total number of particles per unit volume reads as
〈𝑁〉 〈𝑛4 〉 1
= + 2 𝑔2/) (𝜍)
𝑉 𝑉 𝜆
〈.& 〉
Note that in the above expression ?
represents the number of particles per unit volume in the ground
@'/% (<)
state and A'
represents the total number of particles per unit volume other than the ground state.

The equation of state for Bosons can now be written as

𝑃𝑉
= − 0 ln11 − 𝜍 𝑒 "# %! 5
𝑘! 𝑇
&
3
𝑃𝑉 4 𝜋 𝑉 %
= 2 ` 𝑝) ln11 − 𝜍 𝑒 "#5 /()8) 5 𝑑𝑝
𝑘! 𝑇 ℎ 4
3
𝑃𝑉 2 𝑉 2/)
= (2𝜋 𝑚 𝑘! 𝑇) ` √𝑡 ln[1 − 𝜍 𝑒 ": ] 𝑑𝑡
𝑘! 𝑇 √𝜋 ℎ 2
4

The integration can be done by parts to obtain

𝑃𝑉 2 𝑉 1 𝑡 2/) ": ]
2 3 𝑡 2/) 𝜍 𝑒 ":
= l ln[1 − 𝜍 𝑒 − ` 𝑑𝑡n
𝑘! 𝑇 √𝜋 ℎ2 𝜆2 3/2 3 4 1 − 𝜍 𝑒 ":

B
𝑃 1 1 3
𝑡 ) " (
= 2 ` "( : 𝑑𝑡
𝑘! 𝑇 𝜆 Γ(5/2) 4 𝜍 𝑒 − 1

𝑃 1
= 𝑔 (𝜍)
𝑘! 𝑇 𝜆2 B/)
Bose-Einstein condensation

The average number of particles of the Bose-gas is

〈𝑁〉 〈𝑛4 〉 1
= + 2 𝑔2/) (𝜍)
𝑉 𝑉 𝜆
<
Where 〈𝑛4 〉 = ("<. In order that 〈𝑛4 〉 to be positive 0 ≤ 𝜍 < 1. Also, 𝑔2/) (𝜍) is monotonically
@'/%(<)
increasing function of 𝜍. Thus, the maximum value that 𝑔2/) (𝜍) can take is 𝑔2/) (1). represents
A'

the total number of particles per unit volume other than the ground state. The maximum particles per
@'/% (() 〈C〉 @'/% (()
unit volume that all the excited states can hold is . If < all the particles can fit in the
A' ? A'

excited states. However, we can see that number of particles that excited states can hold decreases as
@'/%(()
temperature goes down, because it is proportional to 𝑇 2/) . As temperature is lowered, eventually, A'
〈C〉
becomes smaller than and the excited states can no longer hold all the particles. The excess particles
?

are pushed to the ground state. It turns out that at low enough temperature, this phenomenon happens
with a spectacular effect. Almost all the particles occupy the ground state. This phenomenon is called
Bose-Einstein condensation. The temperature, below which the ground state begins to be populated,
can be determined from the following critical condition

〈𝑁〉 1
= 2 𝑔2/) (1)
𝑉 𝜆
Thus, the transition temperature is given by
)/2
ℎ 〈𝑁〉/𝑉
𝑇D = r s
2𝜋 𝑚 𝑘! 𝑔2/) (1)

At temperatures below 𝑇D more and more particles go to lowest energy state. If one keeps the
temperature fixed, and decreases to volume to increase the density of the gas, the following equation
can also be interpreted as defining a critical particle-density above which the Bose-Einstein
condensation begins. Thus, we can write, for the critical particle-density

〈𝑁〉 1
r s = 2 𝑔2/) (1)
𝑉 D 𝜆
The average number of particles of the Bose-gas can be expressed as

𝑔2 (𝜍)
)
𝑛 = 𝑛4 +
𝜆2
𝑔2 (𝜍)
𝑛4 = 𝑛 t1 − ) 2 u
𝜆

𝑔2 (𝜍)
𝑛
= 1 − ) 2
𝑛4 𝑛 𝜆

At the maximum occupancy, i.e., 𝜍 = 1, the above expression can be expressed as

𝑛 𝜆D 2
= 1 − 2
𝑛4 𝜆
@' (<E()
Where 𝜆D 2 = %
.
. In terms of temperature, the above expressions can be written as
2
𝑛 𝑇D )
= 1 − v w
𝑛4 𝑇