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Classical Statistical Mechanics:

Paramagnetism in the
Canonical Ensemble
Paramagnetism
• Paramagnetism occurs in substances where the
individual atoms, ions or molecules possess
a permanent magnetic dipole moment.
• The permanent magnetic moment is due to
the contributions from:
1. The Spin (intrinsic moments) of the electrons.
Paramagnetism
• Paramagnetism occurs in substances where the
individual atoms, ions or molecules possess
a permanent magnetic dipole moment.
• The permanent magnetic moment is due to
the contributions from:
1. The Spin (intrinsic moments) of the electrons.
2. The Orbital motion of the electrons.
Paramagnetism
• Paramagnetism occurs in substances where the
individual atoms, ions or molecules possess
a permanent magnetic dipole moment.
• The permanent magnetic moment is due to
the contributions from:
1. The Spin (intrinsic moments) of the electrons.
2. The Orbital motion of the electrons.
3. The Spin magnetic moment of the nucleus.
Some Paramagnetic Materials
• Some Metals.
• Atoms, & molecules with an odd number
of electrons, such as free Na atoms,
gaseous Nitric oxide (NO) etc.
• Atoms or ions with a partly filled inner
shell: Transition elements, rare earth &
actinide elements. Mn2+, Gd3+, U4+ etc.
• A few compounds with an even number
of electrons including molecular oxygen.
Classical Theory of Paramagnetism
• Consider a material with N
magnetic dipoles per unit
volume, each with moment .
• In the presence of a magnetic
field B, the potential energy
of a magnetic dipole is:
V   B (minimum) when   0

• This shows that the


dipoles tend to line up B = 0 B ≠ 0
M=0 M≠0
with B.
• The effect of temperature is to randomize
the directions of the dipoles.
• The effect of these 2 competing processes
is that some magnetization is produced.
• Suppose that B is applied along
the z axis, so that  is the angle
made by the dipole with the z
axis as shown in the figure.
•The Canonical Ensemble Probability of
finding the dipole along the  direction is
proportional to the Boltzmann factor f():
• The Canonical Ensemble Probability
of finding the dipole in the  direction
is proportional to:

• The average value of z then is given by:

z 
  f ( )d
z

 f ( )d
• The integration is carried out over the solid
angle with element d. It thus takes into
account all possible orientations of the dipoles.
• To do the integral, substitute
z =  cos & d = 2 sin d
which gives:
 B cos  B cos

  cos  2 sin e kT
d   cos  sin e kT
d
z  0
 B cos
 0
 B cos

 2 sin e kT
d  sin e
0
kT
d
0


B   cos  sin e a cos d
Let a So:
kT
z  0

 sin e d
a cos

0

  cos  sin e a cos d
B
Let a z  0

kT
  d
a cos
sin e
0

• Let cos = x, then sin d = - dx & limits -1 to +1


1
  xeax dx
z  1
Then: 1

 dx
ax
e
1

e  e 1 a a
And:   z     
a
e  e
a
a
• So, the mean value of z has the form:
B  ea  ea 1
[a  ] z    a a
 
e  e
kT a

coth( a ) “Langevin
Function” L(a)
So: z  1
  coth( a )  
 a
• The mean value of z is thus: Langevin Function, L(a)
 ea  ea 1  1
z    a a
  z   coth( a )  
e  e a  a
B
coth( a ) [a  ]
kT

• In most practical situations, a < < 1, so


a  2B
3
a a 2 a5 a
L( a )      L(a ) 
3 45 945 3  z   
3 3kT
• So, in this limit, the approximate magnetization is
N B 2 N = Number of
M  N z  dipoles per unit
3kT volume
• The mean value of z : Langevin Function, L(a)
B  1
[a  ] z   coth( a )  
kT  a
• For small a < < 1 Variation of
a L(a) with a.
L(a ) 
3
a  2B
 z   
3 3kT
• In this limit, the
magnetization is
N 2 B
M  N z 
3kT
• For small a < < 1
N B
2
N 0 H
2 M N0  2
M  N z    
3kT 3kT H 3kT
• This is known as the “Curie Law”. The susceptibility 
is referred as the Langevin paramagnetic susceptibility.
• It can be written in C
in a simplified form as: 
T

N0  2
where, C 
3k

Curie constant
• All of this was obtained using the Canonical
Ensemble & treating the magnetic dipoles classically.
• Our results are that the magnetization has the form:
 1 B
M = N z with z   coth( a )   [a  ]
l  a kT

• By contrast, earlier, we used the Canonical Ensemble


& treated the magnetic dipoles quantum
mechanically assuming spin s = ½ . We found that the
magnetization in this case has the form:
B
M  N   N tanh x x
kT
• The magnetization M & its dependence on the
dimensionless energy ratio B ax
x
are obviously not the same kT
for the two cases. However, it is worth noting that the
function M(x) displays similar qualitative behavior as
a function of x in the two cases.
• The magnetization M & its dependence on the
dimensionless energy ratio B ax
x
are obviously not the same kT
for the two cases. However, it is worth noting that the
function M(x) displays similar qualitative behavior as
a function of x in the two cases.
• Specifically, in the small x limit, (low B, high T), in
both cases, the magnetization simplifies to M = B
where  is called the magnetic susceptibility.
• The magnetization M & its dependence on the
dimensionless energy ratio B ax
x
are obviously not the same kT
for the two cases. However, it is worth noting that the
function M(x) displays similar qualitative behavior as
a function of x in the two cases.
• Specifically, in the small x limit, (low B, high T), in
both cases, the magnetization simplifies to M = B
where  is called the magnetic susceptibility.
• It can be written in the “Curie Law” form
C N0  2 Further, C has the same
 where, C 
T 3k form in both models!!
• So, both the Classical Statistics model & the B
x
Quantum (spin s = ½) model give the SAME kT
magnetization M & in the small x limit, (low
ax
B, high T). That is, both cases give M = B.
• Also, the susceptibility  has the Curie “Law” form:
C N0  2
 where, C 
T 3k
• So, both the Classical Statistics model & the B
x
Quantum (spin s = ½) model give the SAME kT
magnetization M & in the small x limit, (low
ax
B, high T). That is, both cases give M = B.
• Also, the susceptibility  has the Curie “Law” form:
C N0  2
 where, C 
T 3k
• Further, both models give the same qualitative result for
the magnetization M in the large x limit, (high B, low T).
• That is, both cases give M  Constant as x . In
other words, for large enough x, in both models the
magnetization M saturates to a constant value called
the Saturation Magnetization.
• A side by side comparison of plots of the magnetization
M as a function of x for the two cases just discussed
illustrate the behavior discussed for both small & large x.
M = B. “Saturation Magnetization”

M = B.
Quantum
(Spin ½ )
Result Classical
Result