Lecture 13

Bragg-Williams Theory
As noted in Chapter 11, an alternative mean-field approach is to derive a free energy, F , in
terms of our order parameter,m, and then minimize F with respect to m.
We begin with a slightly different definition for m,
m=

(N N )
N

(13.1)

where N = N + N is the total number of sites in the lattice.

The entropy associated with a given m is just the logarithm of the total number of configurations with a given N and N ,

N
S = kB ln
N

N!

= kB ln
(13.2)
N (1+m)
N (1m)
!
!
2
2
Applying Stirlings approximation, the above equation reduces to,

N (1 + m)
N (1 + m)
N (1 + m)
S = kB [N ln N N {
ln

2
2
2

N (1 m)
N (1 m)
N (1 m)
+
ln
}]

2
2
2
N (1 + m)
N (1 + m) (1 + m)
= kB [N ln N N {
ln N +
ln
2
2
2
N (1 + m) N (1 m)
N (1 m) (1 m) N (1 m)

+
ln N +
ln

}]
2
2
2
2
2
N (1 + m) (1 + m) N (1 m) (1 m)
= kB
ln

ln
2
2
2
2
and hence,

1
1
S
= kB ln 2 (1 + m) ln(1 + m) (1 m) ln(1 m)
s(m)
N
2
2

(13.3)

LECTURE 13. BRAGG-WILLIAMS THEORY

87

which is just the entropy of mixing.

To calculate this average, we have to evaluate the Hamiltonian
What is the mean energy, E?
recognizing that the spins interact with each other. In the mean field spirit, as we saw for the
Weiss Molecular field theory, we replace i in the Hamiltonian with its position independent
average, m:
X
1
E = J
m2 = JN qm2
(13.4)
2
hiji

where, again, q = 2d is the lattice coordination number or the number of nearest neighbour
sites for a d-dimensional hypercubic lattice.
Let us now write down the free energy for this system, we have:
F (T, m)
E TS
=
N
N
1
1
= Jqm2 + kB T [(1 + m) ln(1 + m) + (1 m) ln(1 m)]
2
2
kB T ln 2

f (T, m)

(13.5)

Expansion of s(m) near Tc

Now, in the vicinity of Tc , m is small (as we have noted before), so we may expand s(m),
and hence f (m), as follows,

1 4s
1 2s
2
m +
m4 + . . .
(13.6)
s(m) = s(0) +
2
4
2! m m=0
4! m m=0
where,

and,

2s
m2

4s
m4

=
m=0

kB
(1 + m)(1 m)

= 2kB

m=0

= kB
m=0

1 m2 + 2m
(1 + m)3 (1 m)3

= 2kB
m=0

Therefore, the entropy is given as,

s(m) = kB

1
1
ln 2 m2 m4 + . . .
2
12

(13.7)

and the free energy becomes,

1
1 2
1
2
f (m) = kB T ln 2 + Jqm + kB T m + kB T m4
2
2
12
or
1
T m4
f (m)
= (T Tc )m2 +
T ln 2
kB
2
12

(13.8)

LECTURE 13. BRAGG-WILLIAMS THEORY

88

It is clear from the above equation that for T > Tc , the minimum in the free energy occurs
for m = 0. For T < Tc , where does the minimum in f (m) occur?
f (m)/k
4T m3
= (T Tc )m +
=0
m
12
3(Tc T )
m2 =
T
or

m= 3

1/2
Tc
1
T

(13.9)

which is the same result as derived for the Weiss Molecular Field theory!
To explicitly see the behaviour of the free energy, as a function of the order parameter m,
in the vicinity of Tc , refer to the following figure,
h=0
F

T>Tc

T=Tc

T<Tc

13.1

Spins in an external field

Let us now consider our system of spins in the presence of an external magnetic field, h,
such that the free energy becomes f f hm. Referring to Eq. 13.5 we have,
1
1
f (T, m) = Jqm2 hm + kB T [(1 + m) ln(1 + m) + (1 m) ln(1 m)] kB T ln 2
2
2
(13.10)
Minimizing the above expression with respect to m we have,

f
1
1+m
= Jqm h + kT ln
=0
m
2
1m

LECTURE 13. BRAGG-WILLIAMS THEORY

89

Solving for h we find,

1
1+m
h = Jqm + kT ln
2
1m

1
m3 m5
= Jqm + kT m +
+
+ . . . , |m| < 1
2
3
5
= Jqm + kT tanh 1m, or

h
Tc
m = tanh
+ m
kT
T

(13.11)

which again is the same result that we obtained from the Weiss Molecular Field Theory
model.

13.2

Critical Behaviour of Mean Field Theories

Using the expression for the average energy, Eq. 13.4 with the mean field result, Eq. 13.9,
we have,
N Jq
E '
3
2

Tc T
T

From this expression, we may calculate the heat capacity as follows,

3N Jq
3N k
E
=
'
Ch |T Tc =

T T Tc
2Tc
2

(13.12)

(13.13)

Since m = 0 for T > Tc , this implies the average energy and, hence, the heat capacity are
zero as we approach Tc from the positive side. The qualitative behaviour of the heat capacity
actually demonstrates a cusp discontinuity, as seen below.
This behaviour is in contrast to more exact theories and experiments which demonstrate a power law dependence of the heat capacity,
Ch = B |T Tc |

(13.14)

LECTURE 13. BRAGG-WILLIAMS THEORY

90

Cv
discontinuity at T

Tc