PH 202 : STATISTICAL MECHANICS

ASSIGNMENT 4, Total Marks:

1. Assuming the Dietrici equation of state,

P (v − b) = kB T exp (−a/kB T v) (1)

• Evaluate the critical constants Pc , vc and Tc of the given system in terms of the pa-
rameters a and b, and show that the quantity kB Tc /Pc vc = e2 /2 ≃ 3.695.
• Show that it yields the same expression for the second virial coefficient B2 as the van
der Waals equation.
• Show that for all values of P and for T ≥ Tc , it yields a unique value of v.
• For T ≤ Tc , show that there are three possible values of v for certain values of P and
the critical volume vc is always intermediate between the largest and the smallest of
the three volumes.
• Show that the Dietrici equation of state yields the same critical exponents as the van
der Waals equation does.
2. Consider a one-dimensional Ising model where every spin (σi = ±1) interacts with every
other spin and is placed in a magnetic field (B). The Hamiltonian is given by
N N
J X X
H=− σi σj − B σi , J > 0 (2)
N i,j=1, i=1
i<j

• First show that the Hamiltonian can be rewritten as

N
!2 N
J X X
H=− σi − B σi (3)
2N i=1 i=1

up to a constant independent of N . Ignore it in the below calculation. Hence conclude

that eigenstates (|{σi }⟩) of this Hamiltonian have definite magnetization (m), where
m = N1 N
P
σ
i=1 i . [1].
• Now compute the canonical partition function Z(T, B, N ).

Hint: Use the Hubbard–Stratonovich transformation (See Wikipedia for more details)
Z +∞
ax2 /2 1 2
e =√ dσe−σ /2a+xσ (4)
2πa −∞
P 2
N
to N
P
to convert σ
i=1 i i=1 σi . You will get

+∞
r Z
NJ
Z(T, B, N ) = dσe−N βf (σ) (5)
2πkB T −∞

where f (σ) is the effective free energy per spin. Find f (σ). Does the above derivation
work for J < 0? [3]
• Take N → ∞ limit and evaluate the integral via saddle point approximation. Show
that it is [1] s  ∗ 
J −N βf (σ ∗ ) ∗ σ J +B
Z= e , σ = tanh (6)
f ′′ (σ ∗ ) kB T
 • Compute magnetization (m) from the free energy and show that they are the saddles
of f (σ). [1]
• Take B = 0. Show that there is a critical temperature (Tc ) where phase transition
happens. It means that for T > Tc , there is zero magnetization, and for T < Tc , there
is a net magnetization. Compute Tc . Plot f (σ) for T > Tc and T < Tc . Comment
on your observation. Take J = 1, kB = 1. How does the plot change if you turn on
non-zero B? [2.5]
• Comment on the symmetry of f (m). Based on it, think of a simpler potential which
describes the same physics for small m. This will lead you to the “Landau-Ginzburg
Theory,” which you will learn in the Advanced Stat-Mech course. [1.5].

Hint: You may found the identity ln(cosh x) = 12 x2 − 1 4

12
x + · · · useful.

3. This is a continuation of the above problem.

• Compute the partition function using mean field approximation and show that it
matches with the above exact expression in eq. (6) in the limit N → ∞. [5]

The following part focuses near the transition point and computes various critical
exponents (α, β, γ, δ). See Pathria for assistance.
• Near T ≈ Tc , m behaves as (1 − T /Tc )β , find β. [0.5]
• For small B ̸= 0, T = Tc , m behaves as B 1/δ , find δ. [0.5]
• Define susceptibility as χ = ∂m
|
∂B B=0
. Near T ≈ Tc , χ behaves as |1 − T /Tc |−γ , find γ.
[1]
• Compute specific heat (c) near T ≈ Tc , B = 0. It behaves as |1 − T /Tc |−α , find α. Is
c continuous at T = Tc ? Determine the order of transition. [2]
• Show that the above critical exponents satisfy the following bounds [1]
(2 − α)(δ − 1)
α + 2β + γ ≥ 2, α + β(δ + 1) ≥ 2, γ ≥ β(δ − 1), γ ≥ (7)
δ+1
• Draw the phase diagram in the m − T plane. [1]
4. Suppose that each atom of a crystal lattice can be in one of several internal states (which
may be denoted by the symbol σ) and the interaction energy between an atom in state σ ′
and its nearest neighbour in state σ ′′ is denoted by u(σ ′ , σ ′′ ){= u(σ ′′ , σ ′ )}. Let f (σ) be the
probability of an atom being in the particular state σ, independently of the states in which
its nearest neighbours are. The interaction energy and the entropy of the lattice may then
be written as
1 X
E = qN u(σ ′ , σ ′′ )f (σ ′ )f (σ ′′ ) (8)
2 ′
σ ,σ ′′

and X
S/N kB = f (σ) ln f (σ) (9)
σ

respectovely. Minimizing the free energy (E − T S), show that the equilibrium value of the
function f (σ) is determined by the equation
X
f (σ) = C exp {−(q/kB T ) u(σ, σ ′ )f (σ ′ )} (10)
σ′

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 where C is the constant of normalization. Further show that, for the special case u(σ ′ , σ ′′ ) =
−Jσ ′ σ ′′ , where the σ can be either +1 or −1, this equation reduces to the Weiss equation,
with f (σ) = 21 (1 + L0 σ)

5. Consider the triangular lattice in figure 1 with the hamiltonian

X
H = −J ⃗i .S
S ⃗j , J > 0 (11)
⟨ij⟩

where S⃗i is a two-dimensional unit vector assigned to site i that can point from the centre
of an equilateral triangle to one of the three corners of the triangle, as shown in the figure.
As the temperature is lowered, this system undergoes a transition to an ordered phase in

Figure 1

which ⟨S⃗i ⟩ = m × ⃗n for all i, where ⃗n is the unit vector in any one of the allowed directions
and m > 0. Using mean-field theory compute the partition function/free energy and ana-
lyze the behaviour near the phase transition. In particular, find the order of the transition
and the critical temperature. Compute the jump in order parameter (m), if any. Which
symmetry is broken? [10]

6.

7.

8.

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