European Master on Nuclear Fusion Science and Engineering Physics (Madrid)

Statistical Physics
Notes on Lecture 3: Statistical ensembles. Juan MR Parrondo (Uni-
versidad Complutense de Madrid)

1 Partition functions of relevant systems

1.1 One point-particle in a volume V
The system has 3 degrees of freedom. The Hamiltonian is:

|p|2
H= , r∈V (1)
2m

1.1.1 Classical case

Partition function:
V √
Z
V |p|2 V
3
Z1 = 3 dp e−β 2m = 3
2πmkT = 3 (2)
h R3 h Λ

where
h
Λ= √ (3)
2πmkT
is the thermal wavelength. For a unit of atomic mass m ' 10−27 kg at
T = 100 K, the thermal wave length is around 10−8 m.

1.1.2 Quantum case

Assuming a cubic container of side L, V = L3 , the eigenstates of the Hamil-
tonian are solutions of the time-independent Schrödinger equation

~2 2
− ∇ ψ(r) = Eψ(r) (4)
2m
vanishing at the walls of the box, i.e. ψ(r) = 0 if x, y, or z = 0 or x, y, or
z = L:  πn x   πn y   πn z 
x y z
ψ(r) = sin sin sin (5)
L L L

1
where nx , ny , nz = 1, 2, . . . are positive integers (negative integers yield the
same states because the sine is an odd function). The corresponding energy
is:
~2 π 2
n2x + n2y + n2z


Enx ,ny ,nz = 2
(6)
2mL
The partition function is:
∞ X
X ∞ X
∞
Z1 = e−βEnx ,ny ,nz (7)
nx =1 ny =1 nz =1

The sum cannot be calculated exactly. Nevertheless, the momentum1 :

~π
pnx ,ny ,nz = (nx , ny , nz ) (8)
L
takes values in a lattice whose unit cell is a cube of side ~π/L and volume
∆p = ~3 π 3 /V . The exponent |p|2 /(2mkT ) is almost constant within this
unit cell if
~2 π 2 h2
= 1⇒ΛL (9)
mkT L2 4mkT L2
In this case, the sum over all possible momenta can be approximated by an
integral

8V ∞
Z Z ∞ Z ∞
V X |p|2 |p|2
−β 2m −β 2m
Z1 = ∆p e ' dpx dp y dpz e
~3 π 3 p h3 0 0 0
Z 2
V |p| V
= 3
dp e−β 2m = 3 (10)
h R3 Λ

where we have used h = 2π~.

1.2 Ideal gas with N particles in a volume V

1.2.1 Classical case
For an ideal gas of N particles:

Z1N VN
ZN = = 3N (11)
N! Λ N!
1
Here |p| is just a change of variable that we make to calculate the sum. Although
it looks like a momentum, notice that p is not the expected value of the momentum
in eigenstate (5). This expected value is zero, because the eigenstates (5) are linear
combinations of states with momentum p and −p.

2
yielding the free energy, for large N :
 
V
+ N = N kT ln(nΛ3 ) − 1
 
F = −kT ln ZN ' −kT N ln 3
(12)
NΛ

where n = N/V is the particle density. The average energy is:

1 ∂ ln Z 3
hHi = − = N kT (13)
β ∂β 2
The equation of state:
∂F N kT
P =− = (14)
∂V V
The heat capacities:
 
∂hHi 3
CV = = Nk (15)
∂T V,N 2
   
∂hHi ∂V 5
CP = = CV + P = Nk (16)
∂T P,N ∂T P,N 2

The Gibbs free energy:

G = F + P V = N kT ln(nΛ3 ) (17)

and the chemical potential:

G
µ= = kT ln(nΛ3 ) (18)
N

1.2.2 Quantum case

It requires Bose-Einstein and Fermi-Dirac statistics. See Lesson 3. When the
thermal wavelength Λ of the gas is much smaller than the average distance
between particles (V /N )1/3 , the quantum ideal gas can be described by the
classical partition function (11). In this case we say that the gas obeys the
Maxwell-Boltzmann statistics.

1.3 Rigid rotor

A rotor is a system of 2 particles. One is fixed at the origin and the other
moves freely on the surface of a sphere of radius R centered at the origin,

3
i.e.: r1 = 0 and |r2 | = R. The system has 2 degrees of freedom and only
kinetic energy. The Hamiltonian can be written in two ways:
!
1 2
p2φ L2
H= pθ + 2 = (19)
2I sin θ 2I

where θ and φ are the angular coordinates of the mobile particle and pθ and
pφ their corresponding momenta; L is the angular momentum and I = µR2
is the moment of inertia, µ = m1 m2 /(m1 + m2 ) being the reduced mass of
the two particles.

1.3.1 Classical case

In the classical case is more convenient to use the first expression of the
Hamiltonian:
p2
Z π Z 2π Z ∞ Z ∞ p2
1 θ
− 2IkT − φ
Zrot = 2
dθ dφ dp θ dp φ e e 2IkT sin2 θ (20)
h 0 0 −∞ −∞
Z π Z 2π √
1 p
= dθ dφ 2πIkT 2πIkT sin2 θ
h2 0 0
8π 2 IkT 2IkT
= = (21)
h2 ~2
The average energy of the rotor is:
∂ ln Zrot
hHi = − = kT (22)
∂β

1.3.2 Quantum case

Exercise 2.

1.4 Harmonic oscillator

The Hamiltonian of the one dimensional harmonic oscillator is:
p2 κx2 p2 mω 2 x2
H= + = + (23)
2m 2 2m 2
where ω 2 = κ/m. The system has 1 degree of freedom.

4
1.4.1 Classical case
The partition function is:
Z Z
1 p2 mω 2 x2
Zvib = dx dp e− 2mkT − 2kT
h R R
√ r
2πmkT 2πkT kT
= 2
= (24)
h mω ~ω
The average energy is
∂ ln Zvib
hHi = − = kT (25)
∂β

1.4.2 Quantum case

The energy levels of the quantum harmonic oscillator are En = (n + 1/2)~ω,
with n = 0, 1, 2, . . ., and non degenerate. The partition function is:
∞
X 1
Z= e−βEn = e−β~ω/2 (26)
1 − e−β~ω
n=0

When β~ω  1, i.e., when ~ω, which is an energy lying between the ground
state and the first excited state, is much smaller than the thermal energy
kT , then:
1 kT
Z' = (27)
β~ω ~ω
which is the classical result (24). For small temperatures β~ω  1,
Z ' e−β~ω/2 + e−3β~ω/2 + e−5β~ω/2 + . . . (28)
which is simply the contributions of the ground an first excited states.

2 Equipartition theorem
An average of the form  
∂H
xi (29)
∂xj
where xi and xj are coordinates or momenta, can be easily calculated in the
canonical ensemble:
  Z
∂H 1 ∂H −βH
xi = dqdp xi e
∂xj Z ∂xj
Z
1 ∂ −βH
= − dqdp xi e (30)
βZ ∂xj

5
Integrating by parts, and assuming the xi e−βH vanishes in the integration
boundaries, we get:
  Z
∂H 1 ∂xi
xi = dqdp e−βH = kT δi,j (31)
∂xj βZ ∂xj

The expression is of particular interest to calculate the average of a

quadratic term ax2i in the Hamiltonian. If xi only appears in the Hamilto-
nian in this quadratic term, then, applying (31) with i = j:

hxi 2axi i = 2a x2i = kT (32)

i.e., each quadratic term ax2i in the Hamiltonian contributes to the average
energy by kT /2. In particular, the average kinetic energy of a system with
N degrees of freedom is N kT /2. This is the case of the mono-atomic ideal
gas with 3N degrees of freedom (13), and the rotor with 2 degrees of freedom
(22). The theorem can also be applied to the potential energy of a harmonic
oscillator. In the one dimensional case, the kinetic energy contributes to
the average as kT /2 and the potential energy contributes also with kT /2,
yielding (25).