Para magnetism

•The permanent magnetic moment results from the

following contributions:
• The spin or intrinsic moments of the electrons.
•The orbital motion of the electrons.
•The spin magnetic moment of the nucleus.
•Paramagnetism is observed in:
Metals
•Atoms and molecules possessing an odd number of
electrons, that is free sodium atoms, gaseous nitric
oxide etc.
 Classical Theory of Paramagnetism

Langevin’s theory of Para magnetism:

(a) In natural conditions

(in the absence of external magnetic field)

Net dipole moment is zero

μ Total =0

Sample
 Langevin’s theory of Para magnetism contd..

(b) In the presence of external magnetic field:

Dipole align themselves along the direction of external applied
magnetic field.

In order to have to
• have a state of lower energy.
B
• the net magnetisation of the sample
become non-zero and parallel to the magnetic field.

• For large magnetic field’s at low temp. the magnetisation

become of the sample become constant. This implies that
saturation is achieved and all the dipoles are aligned
along the direction of Magnetic Field.
 Langevin’s theory of Para magnetism contd..

The theoretical explanation for the same was given

by Langevin’s on the basis of Boltzmann’s classical
statistics.
acc. To this theory each atom consists of a
permanent magnetic dipole moment μ.
μ
Therefore component of
μ along the field direction is θ

μ Cos θ B

One atom case

 Langevin’s theory of Para magnetism contd..

The magnetic potential energy of the atom in the magnetic field

is
W=-μ.B = - μB cos θ.---(1)

then acc. To Boltzmann classical statistics, the number of atoms

having P.E. in the range

W W+ dW is

W
− dW
dn = Ce kT
Langevin’s theory of Para magnetism contd..

W
− dW
dn = Ce kT
− − − − − − − − − (2)
substituting the value of W and dW
µB cosθ
µB sin θ dθ as W = − µB cos θ 
dn = Ce kT
− − − − − −(3) dW = µB sin θdθ 
 
Now total number of atoms of the specimen
as a whole having energy range W to W + dW
can be calculated by int egrating over all
possible orientations of θ from 0toπ .
π
n = ∫ dn = ∫ Ce µB cosθ / kT µB sin θ dθ − − − −(4)
0
 Langevin’s theory of Para magnetism contd..
π
n = ∫ dn = ∫ Ce µB cosθ / kT µB sin θ dθ this implies
0

n
C= π
− − − − − − (5)
∫
µB cosθ / kT
e µB sin θ dθ
0

as each atom contributes µ cos θ along the direction of magnetic field

thus total magnetisation ofthe sample in the presence of magnetic field is
π
M = nµ cos θ = ∫ Ce µB cosθ / kT µB sin θ µ cos θdθ − − − − (6)
0
π
n
or = π
× ∫ e µB cosθ / kT µB sin θ µ cos θdθ − − − − (7)
∫
µB cosθ / kT
e µB sin θ dθ 0

0
Langevin’s theory of Para magnetism contd..
π
n
M= π
× ∫ e µB cosθ / kT µB sin θ µ cos θdθ
∫
µB cosθ / kT
e µB sin θ dθ 0

0
π

∫
µB cosθ / kT
e sin θ cos θdθ
or M = nµ 2 B 0
π

∫
µB cosθ / kT
e µB sin θ dθ
0

µB
now let us write = x and cos θ = y so that − sin θ dθ = dy
kT
−1

∫ ydy as θ = 0, y = 1
xy
e
thereforeM = nµ +−11 and as θ = π 
 
∫ dy  y = −1 
xy
e
+1
 Langevin’s theory of Para magnetism contd..

−1 xy −1 −1
ye e xy
∫ ydy
e xy
− ∫ dy
x x
As M = nµ +−11 = nµ 1 1
xy −1
e
∫ dy
xy
e
+1 x 1
−1
 e e  e 
−x x xy

− x − x  −  x 2 
1 x −x
− e + e − 2 e − ex
1 −x
[ ] [ ]
or M = nµ    1 = nµ x x
e−x e x
− −
1 x −x
x
e −e [ ]
x x
[
x −x
e +e − e −e
1 x −x
x
] [  e x
+ e
]
−x
1  1
⇒ M = nµ = µ − = µ −
e x − e−x [ n
]
 x −x
 e − e x


n  coth x
x 
Langevin’s theory of Para magnetism contd..

Now as component of magnetic dipole moment of each atom

along B is μcosθ and when dipole moment is fully aligned
along the direction of applied magnetic field then it is only μ
as θ=00
 1  1
M = nµ coth x −  = M s coth x − 
 x  x μ
M
M = M s [ L( x)] ⇒ = [ L( x)]
Ms B
Case I :
µB
For l arg e values of x =
kT
M
= 1 confirms saturation.
Ms
Langevin’s theory of Para magnetism contd..

Case-II For small values of x the curve is linear and coincides

with the tangent to the curve at the origin.

M  1
= coth x −  on exp anding coth x
Ms  x
 1 x x3 1 x
M = M s  + − .... −  = nµ  
 x 3 45 x 3
ignoring higher values of 
 x for small value of x 
 
 µB  nµ B nµ µ 0 H
2 2
M = nµ   = =
 3 kT  3kT 3kT
Langevin’s theory of Para magnetism contd..

nµ 2 µ 0 H
now as M =
3kT
M nµ 2 µ 0 M s2 µ 0 C
therefore χ = = = =
H 3kT 3nkT T
this is called as Curie' s Law and
nµ 2 µ 0 M s2 µ 0
C= = is called as Curie' s cons tan t.
3k 3nk
1
as χ ∝
T
 Langevin’s theory of diamagnetism
The magnetic moment associated with the orbital motion of
electron is related to the corresponding angular momentum L
through the relation.

ρ
 e  y
µ = − L
 2 m  r

In accordance with the Faraday law

d
∫ Edl = −
ORBIT
∫ B.dS
dt ORBIT

d
dt
( B.πr 2 )
E ( 2πr ) = − N
N
r S

1 dB
∴E=− r B
2 dt
One e
 Langevin’s theory of diamagnetism contd..

• The induced electric field exerts a torque = − eEr on electron,

which in turn produces a change in angular momentum in
accordance with the equation
dL
τ=
dt
dL
−eEr =
dt
 1 dB  dL
−e− r r =
 2 dt  dt
The change in angular momentum ∆L
of electron during the magnetic field changes from 0 to B
is obtained by integrating above equation. Thus
1 2
∆L = er B
2
 Langevin’s theory of diamagnetism contd..

This change in angular momentum produces change in magnetic

moment
 e  e2 B 2
∆µ = − ∆L = − r
 2 m  4 m

e2 B Z 2 Where Z is the number

∆µ ATOM =− ∑
4m i =1
ri of e in the atom

e2 B Average radial distance

=− Z r2
4m of e in the atom
Any
arbitrary ρ 2 = x2 + y2 + z2 Spherical
orbit radius symmetrical
1 2 2 2
x2 = y2 = z 2 = ρ ∴ r 2
= x 2
+ y 2
= ρ
3 3
 Langevin’s theory of diamagnetism contd..

• the expression for magnetic moment

induced in atom
Ze 2 B 2 2
µ ATOM =− ρ
4m 3
Ze 2 B 2
=− ρ
6m

there are N atoms per unit volume, the magnetization

induced in the specimen is 2
NZe B 2
M = Nµ ATOM = − ρ
6m

The diamagnetic susceptibility of the specimen is

M µ 0 HNZe 2 2 µ 0 NZe 2 2
χ= =− ρ =− ρ
H 6mH 6m
 Quantum Theory of Paramagnetism

• Classical theory : The energy of a system is varied continuously.

θ =All values of angle are possible.
•Quantum theory : The change of energy is discrete i.e θ is discrete
θ = θ 1 ,θ 2 ,θ 3 ⋅ ⋅ ⋅

For each j only

2j+1 projections

. Space quantization
Only certain particular directions in space is possible.
⇒ It is expressed in terms of angular momentum
rather than magnetic moments.
• Spectroscopic spliting factor(g)
 g:spectroscopic splitting factor
orbital motion : g=1,
spin motion : g=2
• Total angular momentum of atoms( J ) h
= J (J +
J 1)
π
J = L+ S
2
h
L = L( L +1)
2 π
L : Total angular momentum of electrons S = S (S +
h
1)
2 π
S : Total angular momentum of spin
• The effective moments( µ eff )
- The net magnetic moments of the
atom
eh
µ eff =g J ( J + 1)erg / Oe
=
4πmc
= −g J µ
B
 Quantum Theory of Paramagnetism contd..
• The component of µ eff in the direction of the applied field
µ = − g mJ µ
z B
mJ : Quantum number associated with J
J, J-1, J-2, ……-(J-2), -(J-1), -J

• Measurement of g J ( J +1) + S ( S +1) − L( L +1)

g =1 +
2 J ( J +1)
For each value of J , mj has 2J+1 orientations
relative to the magnetic field. The potential
energy of such a magnetic dipole in the
presence of magnetic field is

W = − µ Z B cos θ or W = m j gµ B B
 Quantum Theory of Paramagnetism
contd..
Acc to Maxwell-Boltzmann distribution the number of atoms having a
particular value of mj is thus proportional to
exp( − m j gµ B B / kT )

Considering a unit volume of the paramagnetic material containing a total of N

atoms the magnetisation in the direction of the field is
 average of magnetic moment component per atom 
M = N ×  
 along B 
 m j gµ B B / kT ( m j gµ B B / kT ) 2 
− m  1 − − − ... 
mj = j
− m j gµ B e
− m j gµ B B / kT mj = j
j
 1! 2! 
M =N ∑ = Ngµ B ∑  
mj = − j e
− m j gµ B B / kT
mj = − j  m j gµ B B / kT ( m j gµ B B / kT ) 2

1 − − − ... 
 1! 2! 
 
Now consider the following two cases
(i ) at normal flux densities and ordinary temperatures
m j gµ B B
<< 1 and we can exp and the series exp ression of the above exp ression
kT
Therefore, the above expression can be approximated as
 m j gµB B 
mj = j
−m j  1 − 
 mj =+ j m = 0
 kT 
M = NgµB ∑ now as ∑
j

mj =− j  m j gµB B  mj =− j

 1 − 

 kT 
mj =+ j
m2 j
mj =+ j
m j =2 ∑
2
J ( J +1)(2 J +1)
and ∑ mj =0 =
mj =− j 3

g 2 µ2 B B J ( J +1)(2 J +1)
kT 3 g 2 µ2 B B
therefore M = N =N J ( J +1)
2 J +1 3kT
µ0 M µ0 g 2 µ2 B
Now χ = =N J ( J +1)
B 3kT
Peff2 µ2 B
or χ = Nµ0
3kT
where Peff is effective number of Bohr Magneton.
Peff = g J ( J +1) THIS EXPRESSION IS IDENTICAL TO THE
CLASSICAL EXPRESSION
 Quantum Theory of Paramagnetism
contd..
m j gµ B B
(ii) At low temperature and strong fields >1
kT
and it is not possible to have a series expansion of the
exponential terms.
after algebraic manipulations we can write the M
value as

gJµ B B
M = NgJµ B BJ ( x) where x = and BJ ( x) is
kT
2J +1 2J +1 1 x
the Brillouin function defined as coth( )x − coth( )
2J 2J 2J 2J
in this case BJ ( x) ≈ 1
therefore M = NgJµ B which implies state of saturation magnetisation
Weiss theory of ferromagnetism
The theory of ferromagnetism put forward by Weiss is centered about
the following two hypothesis:
• A specimen of ferromagnetic material contains a number of small
regions called domains which are spontaneously magnetized. The
magnitude of spontaneous magnetization of the specimen as a
whole is determined by the vector sum of the magnetic moments of
individual domains.
• The spontaneous magnetization of each domain is due to the
presence of an exchange field, BE, which tends to produce a
parallel alignment of the atomic dipoles. The field BE is assumed to
be proportional to the magnetization M of each domain, i.e.,
BE = λM
whereλ is a constant called the Weiss – field constant and is
independent of temperature.
 The effective magnetic field on an atom or ion becomes
Beff = B + BE = B + λM
Consider a ferromagnetic solid containing N atoms per unit volume
each having a total angular momentum quantum number J.
M = NgJµ B BJ ( x ) − − − (1)

2J + 1  ( 2 J + 1) x  1  x 
where BJ ( x ) = coth  − coth  
2J  2J  2J  2J 

x ≡ gJµ B Beff k B T
= gJµ B ( B + λM ) k B T
In case of spontaneous magnetization, B=0 so above equation becomes
x ≡ gJµ B λM k BT
xk BT
∴ M (T ) = − − − (2)
λgJµ B
As T → 0 or x → ∞, B J ( x ) → 1 ; the magnetic moments align themselves
parallel to the field and the magnetization M becomes the saturation
magnetization, M S ( 0 ) . Thus, we get

M S ( 0 ) = NgJµ B − − − (3)

From equations (2) & (3), we get

M (T ) xkT
= − − − ( 4)
M S ( 0 ) λNg J µ B
2 2 2

From equations (1) & (3), we get

M (T )
= BJ ( x ) − − − (5)
M S ( 0)
 M (T ) T>Tc T=Tc T<Tc

M S ( 0)
Plot of
Plot of eqn. (5)
eqn. (4)
0 x
Graphical solution of the simultaneous equations (4) and (5). A point of intersection
determines the spontaneous magnetization Ms(T) at a given temperature. No solution
exists for T>Tc.
M/Ms
1

0
T/Tc 1
Spontaneous magnetization versus temperature for T< Tc
paramagnetic region

For T>Tc, the spontaneous magnetization is zero and an

external field will have to be applied to produce some
magnetization. This field should, however, be weak enough
to avoid the saturation state. In such a state, we find that
x<<1 and we can write
 J +1
BJ ( x) ≅  x
 3J 
So, expression (1) becomes
M = Ngµ B ( J + 1) x 3

gJµ B ( B + λM )
x=
k BT

Ng 2 µ B J ( J + 1)
2

Thus, M= ( B + λM )
3k B T
 Which gives
µ 0 M µ 0TC / λ C
χ= = ---(6)
=

B T − TC T − TC

µ 0 TC
where C=
λ

λNg 2 µ B J ( J + 1)
2

and TC =
3k B

The expression (6) is called Curie-Weiss law,

Weiss theory is a good phenomenological theory of magnetism,
But does not explain source of large Weiss field.

Heisenberg and Dirac showed later that ferromagnetism is

a quantum mechanical effect that fundamentally arises from
Coulomb (electric) interaction.
 Magnetic hysteresis
• Hysteresis is well known in ferromagnetic
materials. When an external magnetic field
is applied to a ferromagnet, the atomic
dipoles align themselves with the external
field. Even when the external field is
removed, part of the alignment will be
retained: the material has become
magnetized.
The relationship between magnetic field strength (H) and
magnetic flux density (B) is not linear in such materials. If the
relationship between the two is plotted for increasing levels of
field strength, it will follow a curve up to a point where further
increases in magnetic field strength will result in no further
change in flux density. This condition is called magnetic
saturation.
From the hysteresis loop, a number of primary magnetic
properties of a material can be determined.

Retentivity - A measure of the residual flux density

corresponding to the saturation induction of a magnetic
material. In other words, it is a material's ability to retain a
certain amount of residual magnetic field when the
magnetizing force is removed after achieving saturation.
(The value of B at point b on the hysteresis curve.)

Coercive Force - The amount of reverse magnetic field

which must be applied to a magnetic material to make the
magnetic flux return to zero. (The value of H at point c on
the hysteresis curve.)
Hard and Soft Magnets