Physics

Paper No. : Solid State Physics

Module : Diamagnetism and Paramagnetism of atom - II

Development Team
Prof. Vinay Gupta, Department of Physics and Astrophysics,
Principal Investigator University of Delhi, Delhi

Dr. A.B. Bhattacherjee, School of Physical Sciences, Jawaharlal

Paper Coordinator
Nehru University, New Delhi

Content Writer Dr. A.B. Bhattacherjee, School of Physical Sciences, Jawaharlal

Nehru University, New Delhi

Prof. Poonam Silotia, Department of Physics and Astophysics,

Content Reviewer
University of Delhi, Delhi

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
Description of Module
Subject Name Physics
Paper Name Solid State Physics
Module Name/Title Diamagnetism and Paramagnetism of atoms - II

Module Id M14

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
Contents of this Unit
1. Introduction
2. Quantum theory of magnetic susceptibility.
3. Diamagnetism
4. Paramagnetism
5. Summary

Learning Outcomes

After studying this module, you shall be able to

 Calculating quantum mechanically the magnetic susceptibility by second order perturbation

theory.
 Calculate diamagnetic susceptibility quantum mechanically.
 Calculate paramagnetic susceptibility for the case J  0 quantum mechanically.

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
1. INTRODUCTION

In the present module, we shall consider the dia- and paramagnetic behaviour of solids. The
contribution of the spin of the electron and its orbital angular momentum about the nucleus to the
magnetic momentum of a free atom gives rise to the paramagnetic contribution to the magnetization,
On the other hand , the change in the orbital moment induced by an applied magnetic field gives rise to
the diamagnetic contribution. In other words, paramagnetic magnetic dipoles and magnetic
susceptibility is positive. A diamagnetic substance on the other hand has negative susceptibility.

2. QUANTUM THORY OF MAGNETIC SUSCEPTIBILITYOF ATOM / ION

Consider a system at T = 0 having N magnetic ions per unit volume. The magnetization is defined as
E0 ( Ba )
M ( Ba )   N (14.1)
Ba

Where E0 ( Ba ) is the ground state energy in the presence of an applied magnetic field Ba .
In case T  0 , the system will be in the excited state En ( Ba ) . In thermal equilibrium at temperature T,
the thermal average of the magnetization of each excited sate energy En ( Ba ) gives the magnetization
as

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
  En
 M n ( Ba ) exp( K BT
)
M ( Ba , T )  n
 En
 exp(
(14.2)
)
n K BT
Where,
En ( Ba )
M n ( Ba )   N (14.3)
Ba

The temperature dependence of the magnetic susceptibility  (T ) is,

M 2F
 (T )  0   0 N 2 (14.4)
Ba Ba

Where F is the Helmholtz free energy and M depends on F as,

F
M  N
Ba (14.5)

The free energy F is defined as,

F E (B )
exp( )   exp( n a ) (14.6)
K BT n K BT
Hence, we need to determine the energy shift induced by a magnetic field in order to calculate the
susceptibility.
The total Hamiltonian of an atom/ ion in an external magnetic field is given as,

1 e
H 
2m i
( pi  ri  Ba )2  g0 B s.Ba
2
(14.7)

Where we take the external magnetic field to be in the z- direction. The first term of equation (14.7) is
the kinetic energy while the second term is the interaction energy due to electron spin. Note that the

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
vector potential A   1 r  Ba and satisfies Ba   A and . A  0 . The change in the Hamiltonian on
2
applying an external field Ba is written as,

e2 2
H  0 ( L  g0 s ).Ba  B0  ( xi2  yi2 ) (14.8)
8m i
Where L   ri  pi .
i

Now let the energy E n changes by En on application of the magnetic field Ba . Second-order
perturbation theory gives En as
2
n H n
En  n H n  
n'  n En  En' (14.9)

Where n is the eigen function of the nth energy state.

Finally substituting H from equation (14.8) into equation (14.9) gives and retaining terms up to
quadratic in B0 gives,

2
n  B Ba ( L  g 0 S ) n e2 2
En   B Ba n L  g0 S n    Ba n  (x2
 yi2 ) n
En  E' i
n'  n n 8m i

(14.10)

We will now apply the above quantum mechanical formalism to understand the origin of diamagnetism
and paramagnetism.

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
3. DIAMAGNETISM

Solids which are made up of ions where all electron shells are filled exhibit diamagnetism. For such
ions,

J 0  L 0  S 0  0 (14.11)

Consequently from the expression for En , we have the ground state energy shift:

e2 2
E0 
12m
Ba 0 r
i
i
2
0 (14.12)

In thermal equilibrium, the susceptibility is given as:

 2 E0
   0 N (14.13)
Ba2

For Z electrons is an ion ,

0 r
i
i
2
0  z r 2 (14.14)

Finally this yield,

 0 Nze2 2
 r (14.15)
6m

This expression which was derived based on quantum mechanics coincides with the one derived
classically.

Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
4. PARAMAGNETISM

Solids composed of ions with partially filled shell exhibit paramagnetism. There are two distinct cases.

(i) J  0 and major contribution to paramagnetism is from the first two terms in relation to
equation(14.10).

(ii) J  0 (e.g. Mn3+ or Cr2+) and the second term (third term) is the only contributor.

Let us consider the first case, we assume that only the lowest (2J+1) states are thermally excited.
Therefore, with the applied magnetic field along the z – direction,

F J
g J B
exp( )   exp( B z a ) (14.16)
k BT J z  J k BT

Where we have used the fact that the energy levels of the system in a magnetic field are

EJ (Ba )    Ba  g B J z Ba (14.17)

Summing the geometrical progression, we have

1 1
 rBa ( J  )   rBa ( J  )
e 2
e 2
exp(  F )   rBa   rBa (14.18)
e 2
e 2

Where   1 and r  g  B
kBT

The magnetization is then evaluated from equation (14.5) as

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Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
 M  NrJBJ ( x) (14.19)

Where BJ ( x) is the Brillouin Function,

2J 1 2J 1 1 1
BJ ( x)  ( ) Coth( x)  Coth( x) (14.20)
2J 2J 2J 2J

 Ba
Where x   rJBa 
k BT

Figure 1: Plot of magnetization versus temperature. Solid line is the theory while the squares are the
experimental points.

In the high temperature limit, x<<1

J 1
BJ ( x)  ( )x (14.21)
3J
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Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II
Hence

c
 (14.22)
T

0 Ng 2 [ J [ J  1]] B2
Where c  is the Curie Constant.
3k B

Expression (14.19)is known as the Curie – Brillouin Law and (14.22) is called Curie law.
The second case of J=0 will be discussed in the next module.

5. SUMMARY

In this module you study

 How to calculate the energy shift induced by an external magnetic field in order to calculate the
magnetic susceptibility.
 How Based on the energy shift results, you learn to calculate the magnetic susceptibility of a
diamagnetic substance and paramagnetic solid with J  0 .

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Solid State Physics

Physics
Diamagnetism and Paramagnetism of atom - II