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Table of contents

The Interaction of Solids with Magnetic Fields

Larmor Diamagnetism
Hunds Rules
Van-Vleck Paramagnetism
Curies Law of Free Ions
Curies Law in Solids
Adiabatic Demagnetization
Pauli Paramagnetism
Conduction Electron Diamagnetism
Nuclear Magnetic Resonance: The Knight Shift
Electron Diamagnetism in Doped Semiconductors

Diamagnetic materials have a weak, negative susceptibility to
magnetic fields.
1. Diamagnetic materials are slightly repelled by a magnetic field
and the material does not retain the magnetic properties when
the external field is removed.
2. In diamagnetic materials all the electron are paired so there is
no permanent net magnetic moment per atom.
3. Diamagnetic properties arise from the realignment of the
electron paths under the influence of an external magnetic field.
4. Most elements in the periodic table, including copper, silver,
and gold, are diamagnetic.

Paramagnetic materials have a small, positive susceptibility

to magnetic fields.
1. These materials are slightly attracted by a magnetic field and
the material does not retain the magnetic properties when the
external field is removed.
2. Paramagnetic properties are due to the presence of some
unpaired electrons, and from the realignment of the electron
paths caused by the external magnetic field.
3. Paramagnetic materials include magnesium, molybdenum,
lithium, and tantalum.



Magnetization density and


1.Magnetization density
At T=0 the magnetization density M(H) of a quantummechanical system of volume V in an uniform magnetic field
H is defined to be:

Where: E0(H) is the ground state energy in the presence of

the field H.
Hence, M(H) depend on the material.

Replace the magnetic Helmholtz free energy F to the energy

E we have shorter formula:

Here F is defined by the fundamental statistical mechanical


2.The Susceptibility
The susceptibility is defined as:

In electromagnetism, the magnetic susceptibility is a

dimensionless proportionality constant that indicates the
degree of magnetization of a material in response to an
applied magnetic field.

Calculate the atomic susceptibility:

General formulation

When we apply the magnetic to material, the energy will be

E = E0n+En
The shift energy is component which make the characteristic of
We find the shift energy is calculated:

3. Susceptibility of insulators with

all shells filled:
Larmor diamagnetism
The simplest application of above result is to a solid composed
of ions will all electronic shells filled. Such an ion has zero
spin and orbital angular momentum in its ground state :

Consequently only the term of position in contributes to the

field-induced shift in the ground state energy:

Then the susceptibility of a solid composed of N such

ions is given by:

This equation is known as Larmor diamagnetic


4. Ground state of ions with

a partially filled shell
Hunds rules

4.1 Russell-Saunders Coupling

To a good approximation, the Hamiltonian of the atom or ion
can be taken to commute with the total electronic spin and
orbital angular momenta, S and L, as well as with the total
electronic angular momentum: J=S+L.
The states of the ion can be described by quantum numbers L,
Lz, S, Sz, J and Jz which are eigenstates of the operators L2, Lz,
S2, Sz , J2, and Jz with eigenvalues L(L+1), S(S+1), Sz , J(J+1)
and Jz.
Since the filled shells have zero orbital, spin, and total angular
momentum, these quantum numbers describe the elesctronic
configuration of the partially filled shell, as well as the ion as a

Hunds First Rule
Out of many states one can form by placing n electrons into
the 2(2l+1) levels of the partially filled shells, those that lie
lowest in energy, have the largest total spin S ( that is
consistent with the exclusion principle.
Note: The largest value S can equal to the largest magnitude
that Sz can have.
If n2l+1, S=n: all electrons can have parallel spins without
multiple occupation of any one-electron level in the shell.
If n=2l+1, S=l+n: two electrons on a shell have opposite spins.
S is reduced form its maximum value by half a unit for each
electron after the (2l+1)th

4.2 Hunds Second Rule

The total orbital angular momentum L of the lowest-lying
states has the largest value that is consistent with Hunds first
rule, and with the exclusion principle. That value equal to the
largest magnitude that Lz can have.
When the shell is precisely half filled, all value of lz must be
assumed, and therefor L=0.
The second half of the shell is filled with electrons with spin
opposite to those in the first half, and therefor the exclusion
principle allows us again to go through the same series of
values for L we traversed in filling the first half.

4.3 Hunds Third Rule

The states of lowest energy can leave (2L+1)(2S+1) possible
states, according to this, total angular momentum J can take all
integral values between |L-S| and |L+S|.
The value J assumes in the states of lowest energy is:

5. Susceptibility of insulations
containing ions with a partially
filled shell:

5.1 If J=0
Consider the atoms with full the change of energy from ground
state. It mean that the shift of energy is given by:

When the solid contain N/V such ions per unit

volume, the susceptibility is

5.2 J0
We only consider the first term of energy because is much
greater than the other two
The ground state is (2J+1)-fold degenerate in zero field
Evaluating and diagonalizing (2J+1)-dimentional square matrix

Follow the Wigner-Eckart theorem

Without the surrounding state vectors:

If only the (2J+1) states in the ground state multiplet will

contribute appreciably to the free energy. The above equation
shows that the first tem in the energy shift as expressing the
interaction (-.H) of the field with a magnetic moment that is
proportional to the total angular momentum of the ion.

Magnetization of a Set of Identical

Ions of Angular Momentum J:
Curies Law

If only the lowest 2J+1 state are thermally excited with

appreciable probability, the free energy:

The magnetization of N ions in a volume V:

Where the Brillouin function Bj(x) is defined by

When H << kBT the small-x expansion

The susceptibility is given


This susceptibility is larger than the temperature-independent

Larmor diamagnetic susceptibility.
When an ion of the shell to the total susceptibility of the solid
completely dominates the diamagnetic contribution from the
other (filled) shell.
Diamagnetic susceptibilities are of order 10-5
At room temperature, paramagnetic susceptibility should be of
order 10-2 to 10-3.

Curies law in Solids

Curies law frequently writes as:

Where p, the effective Bohr magneton number, is given:

Thermal properties of
Paramagnetic insulators:
adiabatic demagnetization

The Helmholtz free energy: F=U-TS

Where U is internal energy
The magnetic entropy S(H,T) is given by:

F only depends on the product H:

The entropy has form:

In the case of S unchanged, H/T cannot change, therefore:

This can be used as a practical method for achieving low

temperatures only in a temperature range where the specific
heat of the spin system is the dominant contribution to the
specific heat of the entire solid.

Susceptibility of metals:
Pauli Paramagnetism

Each electron will contribute (taking g=2):

-B/V if its spin is parallel to the field H
B/V if antiparallel
If n is the number of electrons per unit volume, the magnetization
density will be:

If the electrons interact with the field only through their magnetic
moments, the shift energy of each electronic level by BH

The magnetization:

The susceptibility is

It is known as the Pauli paramagnetic susceptibility and in case

of conduction electron is essentially independent of temperature.
In the free electron case, the density of level has form:

Conduction electron diamagnetism

There are also diamagnetic effects arising from the coupling of
the field to the orbital motion of the electrons.
The dependence of M on H doesnt average out to zero. There
is a net nonvanishing magnetization antiparallel to H, known
as the Landau diamagnetism
For free electrons:

Electron diamagnetism in doped

Doped semiconductors is one kind of conducting material which
has conduction electron diamagnetism can be larger than
Consider the case in which the carries go into bands with spherical
symmetry, so that (k)=2k2/m*
This is proportional to m for free electrons, the Pauli susceptibility
of carriers will be reduced by m*/m ( 0.1 or smaller)
As a result:

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