Applications

of the Canonical
Ensemble:
Simple Models
of Paramagnetism
A Quantum System
of Spins J
 Paramagnetic Materials: Spin J
•Consider a solid in which all of the magnetic
ions
are identical, having the same value of spin J.
•Every value of Jz is equally likely, so the
average value of the ionic dipole moment is
zero.
•When a magnetic field is applied in the
positive z direction, states of differing values
of Jz will have differing energies and differing
probabilities of occupation.
The equation for the magnetic moment of an atom
is: Jz
 z   g B   g B M J


Where g is the Lande’ splitting factor given as,

J ( J  1)  S ( S  1)  L( L  1)   
g  1 here, J  L  S
2 J ( J  1)

 e   e 
L  - L S  - S
Also 2m m

 e 
 J  -g J
2m
 Let N be the number of atoms or ions/ m3 of a
paramagnetic material.
The magnetic moment of each atom is,
 e 
 J  -g J
2m
In presence of magnetic field,
according J is quantized J z  M J

Where MJ = –J, -(J-1),…,0,…(J-1), J

i.e. MJ will have (2J+1) values.
If the dipole is kept in a magnetic field B then potential
energy of the dipole is:
 
V    Jz  B    Jz B

 V   M J g B B

In the Canonical Ensemble, the mean magnetic moment at

temperature T is formally:
J M J g B B

M J g B e kT

 J
J M J g B B

e
J
kT
Therefore, magnetization is:
J M J g B B

M J g B e kT Let,
 M  N  N J
M J g B B g B B
J
x
e
J
kT
kT

J J
M J g B e MJx
 J
M e MJx

M N J
J  Ng B J
J
e
J
MJx
 e MJx

J

J
d
 M  Ng B [ln  e ]
MJ x

dx J
 J
d
M  Ng B [ln  e M J x ]
dx J

Mj = -J, -(J-1),….,0,….,(J-1), J, therefore,

d
M  Ng B [ln(e Jx  e ( J 1) x  .....  e  Jx )]
dx
d
 M  Ng B [ln e Jx (1  e  x  .....  e  2 Jx )]
dx
Simplifying this
1 ( 2 J  1)
sinh( J  ) x sinh x
d 2 ]  Ng d 2
M  Ng B [ln B [ln ]
dx x dx x
sinh sinh
2 2
2J  1 (2 J  1) 1 x
M  Ng B [ coth x  coth ]
2 2 2 2
 d
 M  Ng B [ln e Jx (1  e  x  .....  e  2 Jx )]
dx
 x ( 2 J 1)
d Jx 1  e
 Ng B [ln e ( x
)]
dx 1 e
d e Jx  e  Jx e  x
 Ng B [ln{ x
}]
dx 1 e
x
Multiplying and dividing log term by e 2

x x

d e Jx e  e  Jx e
2 2
 Ng B [ln{ x x
}]
dx 
e e 2
2

d e ( J 1 / 2 ) x  e  ( J 1 / 2 ) x
 Ng B [ln{ x / 2
}]
dx e x/2
e
1
sinh( J  ) x
d 2
 Ng B [ln ]
dx x
sinh
2
 2J  1 (2 J  1) 1 x
M  Ng B [ coth x  coth ]
2 2 2 2

2J  1 (2 J  1) 1 xJ
 M  Ng B J [ coth xJ  coth ]
2J 2J 2J 2J

Let a = xJ, above equation may be written as,

2J  1 (2 J  1) 1 a
M  Ng B J [ coth a coth ]
2J 2J 2J 2J
g B B
x
 M  Ng B JB J (a ) kT
gJ B B
a
Here, BJ(a) = Brillouin function. kT

2J  1 (2 J  1) 1 a
B( J )  coth a coth
2J 2J 2J 2J
 Brillouin Function
As a result of these probabilities, the average dipole moment is
given by  J
  g B M J e  BM J B / kBT
M J  J
z  J
 g B J  J ( g B JB / k BT )
 e  g B M J B / k BT

M J  J

2J  1   2 J  1 x  1  x 
where  J ( x )  coth   coth  
2J  2J  2J  2J 

M  n z  ng B J  J ( g B JB / k BT )
 M  Ng B JBJ (a )
The maximum value of
magnetization is
M s  Ng B J
Thus,
2J  1 (2 J  1) 1 a
M  M s[ coth a coth ]
2J 2J 2J 2J
M
 M  M s BJ (a )   BJ (a )
Ms

For J = 1/2

For J = 
M a2
 tanh a  a   ....
M 1
Ms 3
 coth a   L( a)
Ms a
 M g B J M J g B B
Special Let J B  1
kT M J g B e kT

case: M N J
M J g B B
J
M J g B B e
J

 M J g B (1 
kT
)
kT J
M N J
J
M J g B B

J
(1 
kT
)

M J g 2B B g 2B B  J
J 2 2 J 2

 g B  M J  
2
M J g B  MJ
kT kT
 M  N J J N J J
M J g B B J
g B J


J
(1 
kT
) J
1 B  M J
kT  J
J J
J ( J  1)(2 J  1)
 M J  0 and MJ  (
2
But 3
)
J J

Thus above equation becomes,

2
g  B B J ( J  1)(2 J  1)
2 2
g B B 2

M 
N
kT
[
3
] M N J ( J  1)
2J  1 3kT
 Thus  j 2  g 2  B 2 J ( J  1)
g 2  B 0 N 0  J
2 2
M C
 N J ( J  1)  
H 3kT 3kT T
2 2 1
Npeff  B  0
 where, peff  g[ J ( J  1)] 2

3kT
C Npeff  B  0
2 2
 where, C
T 3k
This is curie law.
J
Further, peff  B   J  peff 
B

Thus Peff is effective number of Bohr Magnetons. C is Curie

Constant. Obtained equation is similar to the relation obtained by
classical treatment.
 N e x e x  e x
 x  N x
B N e  e x M   N  N    N  tanh x
e  e x
x
k BT N ex
 x High T ( x << 1 ): N 2 B
N e  e x M  N x 
kB T

Curie-Brillouin law:
g J B B
M  N g J  B BJ  x  x
kB T

Brillouin function:
2J 1   2 J  1 x  1  x 
BJ  x   ctnh    ctnh  
2J  2 J  2 J  2 J 
 g J B B
M  N g J  B BJ  x  x
kB T

1 x x3
High T ( x << 1 ): ctnh x    
x 3 45

M N J  J  1 g  B N p 2  B2 C
2 2
 Curie
  
B 3 k BT 3 k BT T law

pg N J  J  1 = effective number of

Bohr magnetons

Gd (C2H3SO4)  9H2O
Brillouin Function
 If g B JB  k BT , then nearly all of the ions will be
in the lowest state. All dipoles will be aligned with the
applied field and the magnetization is said to be
saturated. The Brillouin function  1 and the
magnetization M  ng B J .

If g B JB  k BT , the ion has nearly the same probability

of being in any of the states and the magnetization will be
small. In the limit of small x , the Brillouin function  (J  1 )x / 3J
and M  13 ng 2 B2 J ( J  1) B / k BT .
The magnetic suspectibility
is
0 M C
 
B T
where
C  13 ng 2 0  B2 J ( J  1) / k B

The Curie constant can be rewritten as C  13 np 0  B / k B

2 2

where p is the effective number of Bohr magnetons per ion.

 The J=1/2 case
Two spins, J=1/2, just two states (parallel
or AP), to average statistically Several similarities

 B exp B B   B exp B B  B B 

 z  g B m J    B tanh 
exp B B  exp B B k BT 

M mJ  B B   B B
  tanhy  tanh 
MS J k BT  k BT

n0 2B

k BT

Estimate the paramagnetic

susceptibility
 Generic J and the Brillouin function
J

m J expm J x
m J  J 1 Z gJ  B B
mJ   , x
J
Z x k BT
 expm x J
m J  J

 ln Z sinh(2J 1) 2x 
M  ngJ  B m J  nk BT Z
B sinh2x 

M  ng J  B JBJ (y)  M S BJ (y)


2J 1 2J 1  1  y  gJ  B JB
BJ (y)  coth y coth , y 
2J  2J  2J 2J  k BT
 Lande’ g-value and effective moment

J 1 J=1/2
BJ (y) 
J=3/2
y
3J J=5

M n0 eff
2

 
MS 3k BT

eff  g J  B J(J 1)

3 S(S 1)  L(L 1)

gJ  
2 2J(J 1) Curie law: =CC/T
(2.828)2χT=g2S(S+1)