MAGNETIC MATERIALS

DKR-JIITN-PH611-MAT-SCI-2010
 Review
1. Relation between B, H and M
A magnetic field can be expressed in terms of Magnetic
field intensity (H) and Magnetic flux density. In free
space, these quantities are related as

B = μ0H (1.1)
In a magnetic material, above relation is written as
B = μH (1.2)

Here μ0 and μ are known as absolute permeability of

free space and absolute permeability of the medium
respectively. The ratio μ/ μ0 is known as relative
permeability of the magnetic material and is
represented as μr.
DKR-JIITN-PH611-MAT-SCI-2010
Magnetization (M)
Magnetization (expressed in ampere/ meter) is defined
as magnetic moment per unit volume. It is proportional
to the applied magnetic field intensity (H).
M = χH (1.3)
Here χ is known as magnetic susceptibility. Further, χ =
μr – 1. χ is expressed in cm-3 . Let us consider equation
(2), B = μH
⇒ B = μ0 μr H = μ0 μr H − μ0 H + μ0 H
⇒ B = ( μ r − 1) μ 0 H + μ 0 H
⇒ B = χμ 0 H + μ 0 H
⇒ B = μ0M + μ0H (1.4)
DKR-JIITN-PH611-MAT-SCI-2010
Classification of magnetic materials
Diamagnetic: Magnetic susceptibility χ is –ve for
diamagnetic materials.
Examples: χ= -3.6 cm-3for Au, -3.2cm-3 for Hg and -
0.2X10-8cm-3 for water)
Paramagnetic: Magnetic susceptibility χ is +ve for
paramagnetic materials but is very small.
Examples: χ = 2.2X10-5 cm-3for Al, 98 cm-3 for Mn

Ferromagnetic: Magnetic susceptibility χ is +ve and

very large for ferromagnetic materials.
Examples: Normally of the order of 105 cm-3.

DKR-JIITN-PH611-MAT-SCI-2010
 2. A microscopic look

In an atom magnetic effect may arise due to:

1. Effective current loop of electrons in atomic

orbit (orbital Motion of electrons);

2. Electron spin;

3. Motion of the nuclei.

 Magnetic moments and angular momentum
1.Orbital Motion
Consider a charge particle moving in a circular orbit
(e.g. an electron around a nucleus), magnetic
moment μ may be given as

qω J
μ = IA = q υ x π r 2
= xπr 2
2π μ
qω r 2 r v
⇒ μ =
2 m,q
r r r r r
But L = r xp = r xm v = mrv = mr 2 ω
r q r
Therefore, μ = L (2.1)
2m
For an electron orbiting around the nucleus, magnetic
moment would be given as
r e r eh
μL = − L = l ( L + 1) (2.2)
2m 2m
Here negative sign shows that μL and L are in opposite
direction. Here,
eh is Bohr Magneton
μB = = 9 . 27 x 10 − 24
2m r
μL e
In the equation (2.2) r = (2.3)
L 2m
is known is orbital gyro-magnetic ratio (γ).
Magnetic moment e
Thus, γ = = (2.4)
Angular mometum 2 m
Equation (2.2) may also be written as
r e r eh
μL = − L = L ( L + 1)
2m 2m
 Magnetic moments and angular momentum

2. Electron spin
Electrons also have spin rotation about their own axis.
As a result they have both an angular momentum and
magnetic moment.

But for reasons that are purely quantum mechanical, the 
ratio between μ to S for electron spin is twice as large as 
it is for a orbital motion of the spinning electron: 

r e r
μ = − S (2.5)
m
3. Nuclear motion

In nuclei there are protons and neutrons which may

move around in some kind of orbit and at the same
time, like an electron, have an intrinsic spin. Again the
magnetic moment is parallel to the angular momentum
and we have

r eh
μ= (2.6)
2m p
 What happens in a real atom?
In any atom, several electrons and some combination of
spin and orbital rotations builds up the total magnetic
moment.

The direction of the angular momentum is opposite to

that of magnetic moment.

Due to the mixture of the contribution from the orbits and

spins the ratio of μ to angular momentum is neither -
e/m nor –e/2m.
⎛ e ⎞
μ = −gJ⎜ ⎟J (2.6)
⎝ 2m ⎠
Where g is known as Lande’s g-factor. gL = 1, gS =2
and 1< gJ <2.
Lande’s g can be obtained from the equation

J ( J + 1) + S ( S + 1) − L ( L + 1)
gJ = 1+ (2.7)
2 J ( J + 1)

Example: If, S = 1, L = 1, J = 0,1, 2

g= 1, 1.5, 1.5
 Diamagnetism
Suppose we slowly turn on a magnetic field in the vicinity
of atom. As the magnetic field changes an electric field is
generated by magnetic induction (Faraday’s law, Maxwell’s
3rd equation).
• From Faraday’s law, the line integral of E around any
closed path is the rate of change of atomic flux through the
path.
d
∫ E .dl = − dt ∫ B .ds B

r dB r
⇒E=− (2.8)
2 dt
e
F
where ∫ds=π r2 and ∫dl=2πr Closed Path Γ
 dL
τ = Fxr = − eEr =
dt

dL er 2 dB This is the extra angular

= momentum from the twist given to
dt 2 dt electrons as the field is turned on.

er 2 er 2
ΔL = ΔB = B Here ∆B = B – 0 = B
2 2
B
This added angular momentum gives
an extra magnetic moment r

e e2r 2
Δμ = − ΔL = − B (2.9) e
2m 4m F
Closed Path Γ
Suppose atomic number be Z, then equation (2.9) may
be written as,

e2∑ r2
Δμ = − B
4m
Where, summation extends over all electrons. Since
core electrons have different radii, therefore
e2Z < r 2 >
Δμ = − B (2.10)
4m
If the orbit lies in x-y plane then,
< r 2 >=< x 2 > + < y 2 >
If r0 represents average radius then

< r0 >=< x 2 > + < y 2 > + < z 2 >

2
For spherical symmetry,
< x 2 >=< y 2 >=< z 2 >

Therefore,
< r 2 >=< x 2 > + < y 2 >= 2 < x 2 > and,

< r0 >= 3 < x 2 >

2

< r0 >
2
3 2
= ⇒< > =< >
2
Thus, r 2
r
< r >
2 0
2 3
Therefore, equation (2.10) may be written as

e 2 BZ 2
Δμ = − ( < r0 > )
2

4m 3
 or,
e 2 BZ < r0 >
2
Δμ = −
6m

If there are N number of atoms per unit volume

then,
NZe 2 B < r0 >
2
M = NΔμ = − (2.11)
6m
and,
M μ 0 NZe 2 < r0 >2
χ = = − (2.12)
H 6m

Equation (2.11) is the Langevin’s formula for volume

susceptibility of diamagnetism of core electrons.
Conclusions
M μ 0 NZe 2 < r0 > 2
χ = = −
H 6m
1. Susceptibility of diamagnetic material is proportional to
the atomic number. Thus bigger the atom larger would
be the susceptibility.
2. Diamagnetic susceptibility depends on internal structure
of the atoms which is temperature independent and
hence the diamagnetic susceptibility.
3. All electrons contribute to the diamagnetism even s
electrons.
Example: r0 = 0.1 nm, N = 5x1028/m3
4πx10−7 x5 x1028 x(1.6 x10−19 ) 2 x(0.1x10−9 ) 2
χ =− = −3 x10 −6

6 x9.1x10−31
 Paramagnetism
• B>B0 , χ is positive, μr>1, .
• The permanent magnetic moment results from the
following contributions:
1. The spin or intrinsic moments of the electrons.
2. The orbital motion of the electrons.
3. The spin magnetic moment of the nucleus.
• Paramagnetism is observed in:
1. Metals
2. Atoms and molecules possessing an odd number of
electrons, that is free sodium atoms, gaseous nitric
oxide etc.
3. A few compounds having an even number of electrons
(example Oxygen molecule)
4. Free atoms or ions having a partially filled inner shell
e.g. rare earth and actinide elements, ions of some
transition elements such as Mn2+
Manganese, platinum, tungsten, some members of
rare earth group and ions formed by removing and
adding electrons to basic atoms there by creating
unpaired spins.
 Paramagnetism has net magnetic moments

No field : M=0 Field is applied, low Temp.

B
Field is applied, and High Temp.
B
χ

T
from http://www.geo.umn.edu
Classical theory of paramagnetism
In presence of magnetic field, potential energy of
magnetic dipole may be given as B μ z = μ cos θ
μ
θ
r r
V = − μ . B = − μ B cos θ

Where, θ is angle between magnetic moment and the

field. From equation it is obvious that
V = − μ B (minimum) when θ = 0

It shows that dipoles tend to line up with the field. The

effect of temperature, however, is to randomize the
directions of dipoles. The effect of these two competing
processes is that some magnetization is produced.
Suppose field B is applied along z-axis, then θ is angle
made by dipole with z-axis. The probability of finding the
dipole along the θ direction is
V μB cos θ
−
f(θ ) = e kT
=e kT

f(θ) is the Boltzmann factor which indicates that dipole is

more likely to lie along the field than in any other
direction.
The average value of μz is given as

μz = ∫ μ f (θ ) d Ω
z

∫ f (θ ) d Ω
Where, integration is carried out over the solid angle,
whose element is dΩ. The integration thus takes into
account all the possible orientations of the dipoles.
Substituting μz = μ cosθ and dΩ = 2π sinθ dθ
μ B cos θ

μz = ∫ μ cos θ 2 π sin θ e kT
dθ
μ B cos θ

∫ 2 π sin θ e kT
dθ B μ z = μ cos θ
μ
θ
μ B cos θ
μ ∫ sin θ cos θ e kT
dθ
⇒ μz = μ B cos θ

∫ sin θ e kT
dθ

1
⇒ μ z = μ coth( a ) − = μ L(a)
v
μB
where a =
kT

Where L(a) is known as Langevin function, expanded

as L (a ) =
a
−
a
3
+
2 a5
− ⋅⋅⋅⋅
3 45 945
 L( a )

From the variation of L(a), it is

clear that at low a and hence
at low field dipole moment is
proportional to B and at high
a i.e. B, it saturates.

In most practical situations a =

μB
kT
a<<1, therefore,
Variation of L(a) with a.
a μ 2B
μz = μ =
3 3kT
The magnetization is given as
Nμ 2 B Where N is the number of
M = Nμ z =
3kT dipoles per unit volume
 Nμ 2 μ0 H
⇒M =
3kT

M Nμ0 μ 2
⇒ =χ=
H 3kT
This equation is known as Curie Law. The susceptibility
is referred as Langevin paramagnetic susceptibility.
Further, contrary to the diamagnetism, paramagnetic
susceptibility is inversely proportional to T

Above equation is written in a simplified form as:

χ=
C
where, C =
Nμ 0 μ 2 χ
T 3k

Here C is known as curie constant.

T
Self study:

1. Volume susceptibility (χ)

2. Mass susceptibility (χm)

3. Molecular susceptibility (χM)

Quantum theory of Paramagnetism
Let N be the number of atoms or ions/ m3 of a paramagnetic
material. Let J be the total angular momentum quantum number
of each atom. The magnetic moment of each atom is given as,
r e r r r
μ J = -g J = − gμ B J J = hJ
2m
Where g is the Lande’ splitting factor which is given as,
J ( J + 1) + S ( S + 1) − L ( L + 1)
gJ = 1+
2 J ( J + 1)
In presence of magnetic field, μJ will precess about the field
such that the component of μJ in the field’s direction is MJμB
(remember space quantization). This may be recalled that
for a J value, MJ will have values from –J, -(J-1),…,0,…(J-
1), J i.e. MJ will have (2J+1) values.
The magnetic moment of an atom corresponding to a given
value of mJ is thus,
μ J = M J gμ B

If dipole is kept in a magnetic field B then potential energy

of the dipole would be
r r
V = − μ J B = − μ J B = − M J gμ B B
Therefore, Boltzmann factor would be,
M J gμ B B

f =e kT

Thus, average magnetic moment of atoms of the

paramagnetic material would be
+J M J gμ B B

∑ M J gμ B e kT

μ = −J
+J M J gμ B B

∑e
−J
kT
Therefore, magnetization would be
+J M J gμ B B

∑M J gμ B e kT

M = Nμ = N −J
M J gμ B B
+J

∑e
−J
kT

gμ B B
Let, x = Therefore,
kT
+J +J

∑ M J gμ B e MJx
∑ J
M e MJx

M =N −J
+J
= Ngμ B −J
+J

∑e
−J
MJx
∑ e MJx

−J

+J
d
⇒ M = Ngμ B [ln ∑ e M J x ]
dx −J
Since Mj = -J, -(J-1),….,0,….,(J-1), J, therefore,
d
M = Ng μ B [ln( e Jx + e ( J −1) x + ..... + e − Jx )]
dx
d
⇒ M = Ng μ B [ln e Jx (1 + e − x + ..... + e − 2 Jx )]
dx
Simplifying this equation, we get (consult Solid State
Physics by S.O. Pillai),
1
sinh( J + ) x
d 2 ]
M = Ng μ B [ln
dx x
sinh
2
2J + 1 ( 2 J + 1) 1 x
M = Ng μ B [ coth x − coth ]
2 2 2 2
 2J + 1 ( 2 J + 1) 1 x
M = Ng μ B [ coth x − coth ]
2 2 2 2

2J +1 ( 2 J + 1) 1 xJ
⇒ M = Ng μ B [ coth xJ − coth ]
2 2J 2 2J

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

2J + 1 ( 2 J + 1) 1 a
M = Ngμ B [ coth a − coth ]
2 2J 2 2J
2J + 1 ( 2 J + 1) 1 a
M = Ng μ B J [ coth a− coth ]
2J 2J 2J 2J

⇒ M = Ngμ B JB J (a )

Here, BJ(a) is known as Brillouin function defined as,

2J + 1 ( 2 J + 1) 1 a
B( J ) = coth a− coth
2J 2J 2J 2J
 M = Ngμ B JBJ (a )

The maximum value of magnetization

would be

M s = Ng μ B J
Thus,
2J + 1 ( 2 J + 1) 1 a
M = M s[ coth a− coth ]
2J 2J 2J 2J

⇒ M = Ms BJ (a)
M
= B J (a )
Ms
For J = 1/2

M a2
= tanha = a − + ....
Ms 3
For J = ∞

M 1
= coth a − = L ( a )
Ms a
 M J gμ B B
Let us consider the case when, M J x << 1 ⇒ << 1
kT
M J gμ B B
+J +J
M J gμ B B
∑ M J gμ B e kT
∑ M J g μ B (1 +
kT
)
M =N −J
=N −J
+J M J gμ B B +J
M J gμ B B
∑e kT
∑
−J
(1 +
kT
−J

+J
M J g 2μB B +J
g 2μB B + J
2 2 2

∑ M J gμ B + gμ B ∑ M J + ∑
2
MJ
kT kT
⇒ M = N −J +J =N −J −J
M J gμ B B +J
gμ B B +J

∑
−J
(1 +
kT
) ∑−J
1 +
kT − J
∑ MJ

+J +J
J ( J + 1)( 2 J + 1)
But ∑ = 0 and ∑ = 2(
2
M J M J )
−J −J 6
Thus above equation becomes,
g 2 μ B B J ( J + 1)( 2 J + 1)
2
g 2μB B
2
N [ ]
M = kT 3 ⇒M =N J ( J + 1)
2J + 1 3kT
Thus
g 2μ B μ0 Nμ0 μ J
2 2
M C
⇒χ= =N J ( J + 1) = =
H 3kT 3kT T

1
Np eff μ B μ 0
2 2

⇒ χ = where, peff = g[ J ( J + 1)] 2

3 kT
C Np eff μ B μ 0
2 2
⇒χ= where, C =
T 3k

This is curie law.

μJ
Further, p eff μ B = μ J ⇒ p eff =
μB

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

Constant. Obtained equation is similar to the relation obtained by
classical treatment.
 How to obtain peff?
1. Find orbital quantum number (l) for partially filled shell. For
example, for iron electronic configuration is
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3 d 6

Thus the only orbital outside the closed shell are 3d6. For d orbital, l =
2.
2. Corresponding to l value, obtain magnetic quantum number ml (l,
(l-1),…..0,….,-(l-1), -l). For example for l = 2, ml = 2, 1, 0, -1, -2.

3. Apply following three Hund’s rules to obtain ground state:

(i)Choose maximum value of S consistent with Pauli exclusion
principle.
(ii)Choose maximum value of L consistent with the Pauli exclusion
principle and rule 1.
(iii)If the shell is less than half full, J = L – S and if it is more than half
full the J = L + S.
For the taken example,

ml 2 1 0 ‐1 ‐2
ms

L = ∑m l = 2 S = ∑m s = 2

4. Obtain J. Since, shell is more than half filled therefore,

J = L+ S = 2+2 = 4
Thus g can be obtained by using formula
J ( J + 1) + S ( S + 1) − L ( L + 1)
gJ = 1+
2 J ( J + 1)
1

Then peff can be obtained by using formula peff = g[ J ( J + 1)] 2

Weiss Theory of Paramagnetism
Langevin theory failed to explain some complicated temperature
dependence of few compressed and cooled gases, solid salts,
crystals etc. Further it does not throw light on relationship between
para and ferro magnetism.

Weiss introduced concept of internal molecular field in order to

explain observed discrepancies. According to Weiss, internal
molecular field is given as

H i = λM

Where λ is molecular field coefficient. Therefore the net effective field

should be
H e = H + λM

But, we know from classical treatment of paramagnetism that

a
M = M s( )
3
 Nμ 2μ0H Nμ 2 μ 0
Or, M = e ⇒ M = (H + λM )
3 kT 3 kT

Nμ 2 μ 0 Nμ 2 μ 0 Nμ 2μ 0 H
⇒ M (1 − λ) = H ⇒ M =
3 kT 3 kT Nμ 2μ 0
3 kT (1 − λ )
3 kT
M Nμ 2 μ 0 Nμ 2 μ 0
⇒χ= = =
H Nμ μ 0
2
Nμ 2 μ 0
3kT (1 − λ ) 3k (T − λ )
3kT 3k

Nμ 2μ 0 Nμ 2μ 0
⇒ χ = ⇒ θc =
3 k (T − θ c ) 3k

θc is known as paramagnetic curie point. Above equation is known

as Curie-Weiss Law.