1

Chapter Eleven Diamagnetism and Paramagnetism

The story of magnetism begins with a mineral called magnetite Fe
3
O
4
.
The first truly scientific study of magnetism was made by William Gilbert.
His book On the magnet was published in 1600.
In 1820 Hans Christian Oersted discovered that
an electric current produces a magnetic field.
In 1825 the first electromagnet was made by Sturgeon.
Each stores the same
magnetic energy ~0.4J .
2
H (Oe)
M

(
e
m
u
/
c
m
3
)
H (Oe)
M

(
e
m
u
/
c
m
3
)
diamagnetism
paramagnetism
ferromagnetism
Magnetic susceptibility per unit volume
H
M

M : magnetization, magnetic moment per unit volume
B : macroscopic magnetic field intensity
In general, paramagnetic material has a positive susceptibility ( >0).
diamagnetic material has a negative susceptibility (<0).
CGS
3
Three principal sources for the magnetic moment of a free atom :
Electrons spin
Electrons orbital angular momentum about the nucleus
Change in the orbital moment induced by an applied magnetic field
First two sources give paramagnetic contributions.
The last source gives a diamagnetic contribution.
1895 Curie proposed the Curie law
1905 Langevin proposed the theory of diamagnetism and paramagnetism
1906 Wiess proposed the theory of ferromagnetism
1920s The physics of magnetism was developed with theories involving
electron spins and exchange interactions the beginnings of QM
1903
1859~1906
P. Curie
4
Reviews, in CGS
H M 4 H B

= + =
V
N
m M

=
: magnetic dipole moment
L L


B
i
i i
2m
e
p r
2m
e
m = =

=
S

o B
i
i o B
g s g m =

=
[emu/cm
3
]
Bohr magneton
Electronic g-factor g
o
=2.0023
2 24 -
B
1Vs/m 1T J/T; 10 9.27
2m
e
= = =

Angular
momentum
Spin
I
v

L and S are quantum operators with no basis in classical physics.
electron
m

5
Theory of diamagnetism
was first worked out by Paul Langevin in 1905.
Motion of the electron is equivalent to current in the loop.
Faradays law
Negative magnetism present in an applied field
even though the material is composed of atoms
that have no net magnetic moment.
dt
d
B
= Emf
[volt]
Consider a circular loop with radius r, the effect of applied field H is
to change by an amount in negative direction.
2
2
2
A
6mc
e
A
N
R
Z
=
[emu/Oe-cm
3
]
I
H

r
1872~1946
Paul Langevin
6
The change in moment of a single orbit :
dt
dH
2
r
dt
dH
r 2
r
dt
dH A
E
2
= = = =

Emf
dt
dH
2mc
er
mc
eE
dt
dv
a = = =

|
.
|

\
|
= dH
2mc
er
dv
H
2mc
er
v =
H
4mc
r e
v
2c
er
2
2 2
= =
the plane of the orbit is perpendicular
to the applied field
R
All possible orientations in the hemisphere
( )( )
2
2 /
0
2
2
2
2
2 2 2 2
3
2
d sin 2 sin
2

A
dA sin
sin r
R R R
R
R
R R
= =
= =

7
A single electron with consideration of all possible oriented orbits,
H
6mc
e
v
2c
e
2
2 2
R R
= =
For an atom that contains Z electrons,

= =
= =
z z
R
R
1 i
2
i
2
2
1 i
2
2
i
2
6mc
H e
H
6mc
e

R
i
is the radius of the ith orbit
Susceptibility,
2
2
2
A
mc 6
e
A
N
R
Z
=
The number of atoms per unit volume : N
A
/A
Avogadros number
Atomic mass
Volume density of mass
H
6mc
e
A
N
1 i
2
i
2
2
A
|
.
|

\
|
=

=
z
R

On the volume basis,

Carbon (radius =0.7)
( ) ( )
( )( )
( )
3 6 -
2
8
2
10 28
2
10 3 23
cm emu/Oe 10 1.5
cm 10 7 . 0
cm/s 10 3 g 10 11 . 9 6
6 esu 10 80 . 4
12.01g
g/cm 22 . 2 10 02 . 6
=

Experimental value : -1.110

-6
emu/Oe-cm
3
Classical Langevin result
8
This classical theory of Langevin is a good example of the use of a simple
atomic model to quantitatively explain the bulk properties of a material.
The agreement between calculated and experimental values for other
diamagnetic materials is generally not that good, but it is at least within
an order of magnitude.
The other consistency is that
is independent of temperature
for most diamagnetic materials.
Quantum theory of diamagnetism
results in the same expression.
Negative susceptibility
magnitude : 10
-5
~10
-6
cm
3
/mole
9
Diamagnetic materials
Closed-shell electronic structures result in no net moment
The monatomic rare gases He, Ne, Ar,
Polyatomic gases, H
2
, N
2
,
Some ionic solids, NaCl,
Some covalent solids, C, Si, Ge,
Superconductors : Meissner effect
The first systematic measurements of susceptibility of a large number
of substances over an extended range of temperature were made by
Pierre Curie and reported by him in 1895.
-- mass susceptibility is independent of temperature for diamagnetics,
but that it vary inversely with temperature for paramagnetics.
T
C
=

=
T
C'
Curie law Curie-Weiss law (1907)
in general
Pierre Weiss
1865~1940
10
Quantum theory of diamagnetism
Hamiltonian V A H Q
c
Q
p
m 2
1
2
+
|
.
|

\
|
=

Terms due to the applied field

( )
2
2
2
2mc
e
mc 2
e
' A A A
i
H + + =

A

= B
In the uniform magnetic field
k

B B=

( )
k

y x
j

x z
i

z y

k

z
j

y
i

x
x
y
z x x z
z y x
|
|
.
|

\
|

+
|
.
|

\
|

+
|
|
.
|

\
|

=
+ +
|
|
.
|

\
|

=
A
A
A A A A
A A A A

One solution k

0 j

2
xB
i

2
yB
+ + = A

( )
2 2
2
2 2
y x
8mc
B e
x
y
y
x
mc 4
B e
' + +
|
|
.
|

\
|

=
i
H
z
L
~
11
z-component of angular momentum
|
|
.
|

\
|

=
x
y
y
x L
~
z
i
paramagnetism
For diamagnetic materials with all electrons in filled core shells,
the sum over all electrons vanishes

+
z z
2S L
For a spherically symmetric system
2 2 2
r
3
2
y x = +
2
2
2 2
2 2
2
2 2
B
12mc
e
y x
8mc
B e
'
r
E = + =
the additional energy
the associated magnetic moment B
6mc
e
B
'
2
2 2
r
E
=

=
in agreement with the classical Langevin result
12
Vibrating Sample Magnetometer (VSM)
measuring samples magnetic moment
oscillate sample up and down
measure induced emf in coils A and B
compare with emf in coils C and D from known magnetic moment
13
14
Classical theory of paramagnetism
In 1905, Langevin also tried to explain paramagnetism qualitatively.
He assumed that paramagnetic materials have molecules or atoms with
the same non-zero net magnetic moment .
In the absence of magnetic field, these atomic moments point at random
and cancel one another. M=0
When a field is applied, each atomic moment tends to align with the field
direction; if no opposing force acts, complete alignment would be
produced and the material demonstrates a very large moment. But
thermal agitation of atoms tends keep the atomic moments pointed at
random. Partial alignment and small positive .
As temperature increases, the randomizing effect of thermal agitation
increases and hence, decreases.
This theory leads naturally into the theory of ferromagnetism.
15
A unit volume material contains n atoms with a magnetic moment each.
cos H H = =

E
T k
cos H
T k
E
B B
d sin 2 dA dn

e K e K = =

=



0
T k
cos H
B
sin d 2 dn n e K

=



0
T k
cos H
0
B
sin cos d 2 cos dn M e K
n
Let a = H/k
B
T,
|
|
.
|

\
|

+
=

a
1
n
dx
dx x n

sin d
sin cos d n
M
a a
a a
1
1
ax
1
1
ax
0
cos a
0
cos a
e e
e e
e
e
e
e

( )
|
.
|

\
|
=
a
1
a coth n
H

Let the direction of each moment be presented by a vector,

and let all vectors be drawn thru. the center of the sphere.
#at angle +d
total #
16
Langevin function L(a)=coth(a)-1/a
a=H/k
B
T
M
/
M
o
L(a) can be expressed in series,
...
945
2a
45
a
3
a
L(a)
5 3
+ =
When a is small (<0.5),
L(a) is a straight line w/. a slope 1/3.
When a is large, L(a) 1.
Two conclusions :
(1)Saturation will occurs at large a implying that at large H and low T the
alignment tendency of field is going to overcome the randomizing
effect of thermal agitation.
(2)At small a, L(a) depends linearly on a implying that M varies linearly
with H.
17
The Langevin theory also leads to the Curie law.
For small a,
T k
H
3
n
3
a n
M
B

= =
T k 3
n
H
M
B
2

= =
T
C
=
B
2
k 3
n
= C
Oxygen is paramagnetic and obeys the Curie law w/. =1.0810
-4
emu/gOe.
B

85 . 2
mole erg/Oe 10 2.64
10 02 . 6
) emu/gOe 10 08 . 1 )( erg/K 10 38 . 1 )( g/mole 32 ( 3
n
T k 3
20 -
23
4 16
B
=
=


= =

Even in heavy atoms or molecules containing many electrons,
each with orbital and spin moments, most of the moments cancel out
and leave a magnetic moment of only a few Bohr magnetons.
Typically,
( )( )
( )( )
0064 . 0
300K erg/K 10 38 . 1
10000Oe erg/Oe 10 64 . 2
T k
H
a
16
20
B
=

= =

smaller enough L(a)=a/3

<0.5
18
The Langevin theory of paramagnetism which leads to the Curie law, is
based on the assumption that individual carrier of magnetic moment do
not interact with one another, but are acted on only by applied field and
thermal agitation.
However, many paramagnetic materials obey the more general law,
considering the interaction between elementary moments.

=
T
C
Curie-Weiss law (1907)
Weiss suggested that this interaction could be expressed in terms of
a fictitious internal field, molecular field H
M
. In addition to H.
The total field acting on material H + H
M
= H + M
T M H
M
H
M
tot
C
=
+
= =

( ) H M T C C =

= =
T T H
M C
C
C
where (=C) is a measure of the strength of the interaction.
19
Theoretical predictions

C C C

= T
1 T 1
Intercept reveals information of
(FeSO
4
)<0, (MnCl
2
)>0
>0 indicates that the molecular field aids the applied field, makes
elementary moments align with H, and tends to increase .
<0 indicates that the molecular field opposes the applied field, makes
elementary moments disalign with H, and tends to decrease .
20
Precession of atomic magnetic moments about H,
like gyroscope, angular momentum in the presence of gravitation.
H

=
dt
L d
m r


= = g
If the atom was isolated, the only effect of an increase in H would be
an increase in the rate of precession, but no change in .
For a system with many atoms, all subjected to thermal agitation,
there is an exchange of energy among atoms. When H is applied,
the exchange of energy disturbs the precessional motion enough so
that the value of for each atom decreases slightly, until the
distribution of values becomes appropriate to the existing values of
field and temperature.
21
Quantum theory of Paramagnetism
The central postulate of QM is that the energy of a system is discrete.
quanta of energy
improving the quantitative agreement
between theory and experiment.

H
J =1/2 J =2
H
Classical case Quantum case
is continuous variable.
is restricted to certain variables.
Space Quantization
22
The orbital and spin magnetic moments for an electron
orbit orbit
p
2mc
e
2 2mc
e
mc 4
e
= = =

h h
spin spin
p
mc
e
2 2
1
mc
e
mc 4
e
= = =

h h
In general
p
2mc
e
g =
where g is spectroscopic splitting factor, or g-factor
g=1 for orbital motion and g=2 for spin
In a multiple-electron atom, the resultant orbital angular momentumand the
resultant spin momentumare characterized by quantum numbers L and S.
Both are combined to give the total angular momentumthat is described by
the quantum number J .
B
g g 1) J(J 1) J(J
mc 2
e
+ = + =
In the direction of H,
B
g g
J J H
m m
mc 2
e
= =
There are 2J +1 numbers of allowed azimuthal quantum number m
J
:
J , J -1, , -(J -1), -J .

H
H
23
For a free atom, the g factor is given by the Land equation
1) 2J(J
1) L(L 1) S(S 1) J(J
1
+
+ + + +
+ = g
The energy levels of the system in a magnetic field
2B
m
s

s
1/2 -
-1/2
H g m H E
B J
= =

For a single spin with no orbital moment, m

J
=1/2 and g=2.
The equilibrium population for the two level system :
) T H/k exp( ) T H/k exp(
) T H/k exp(
N
N
) T H/k exp( ) T H/k exp(
) T H/k exp(
N
N
B B
B 2
B B
B 1




+

=
+
= lower level
upper level
Total number of atoms
is conserved.
N = N
1
+N
2
= constant
24
The resultant magnetization for N atoms per unit volume
( ) x tanh N N ) N (N M
x x
x x
2 1
=
+

= =

e e
e e
where
T k
H
x
B

=
For x<<1, tanh(x)~x and
T k
H
N x N M
B
2

=
For a system with known g and J ,
Potential energy of each moment in H
H g m U
B J
=
The probability of an atom w/. energy U
T H/k g m T U/k
B B J B

e e =

Therefore,
Boltzmann statistics

=
J
B B J
J
B B J
m
T H/k g m
m
T H/k g m
B J
g m
N M

e
e
( )
(x) B J N
2J
x
coth
2J
1
2J
x 1 2J
coth
2J
1 2J
J N M
J B
B

g
g
=
(

|
.
|

\
|

|
.
|

\
|
+ +
=
Brillouin function
where
T k
H J
x
B
B
g
=
m
J
: J , J -1, , -(J -1), -J
25
The saturation magnetization
B H o
J N N M g = =
Number of atoms
per unit volume
The maximum moment of each
atom in the direction of H
( )
|
.
|

\
|

|
.
|

\
|
+ +
= =
2J
x
coth
2J
1
2J
x 1 2J
coth
2J
1 2J
(x) B
M
M
J
o
Brillouin function, 1927
When J =, the classical distribution,
the Brillouin function reduces to the
Langevin function.
( )
x
1
x coth
M
M
o
=
When J =1/2, the magnetic moment
consists of one spin per atom.
( ) x tanh
M
M
o
= x
x<<1
T k
H
N
T k
H
J Ng x N M
B
2
B
2
B
2 2
H

= =
26
The Brillouin function, like the Langevin, is zero for x equals to zero
and tends to unity as x becomes large. The course of the curve in
between depends on the value of J for the atom involved.
T k
H
x
B

=
classical
T k
H
T k
H J
x
B
H
B
B

= =
g
quantum

: net magnetic moment in

the atom
KCr(SO
4
)12H
2
O
Henry, Phys. Rev. 88, 559
(1952)
27
When H is large enough and T low enough, a paramagnetic can be saturated.
For example, KCr(SO
4
)12H
2
O at H=5Tesla and T=4.2K
only magnetic ion Cr
3+
, J =3/2, L=3, and S=3/2 g=2/5
the lower curve shown in the figure
data does not follow this predicted curve
The data is well described by the quantum model with J =S=3/2 and g=2 .
B B
1) J(J J + = = g g
L=0 no orbital component
B B
87 . 3 1)
2
3
(
2
3
2 = + =
Spin-only moment
28
Gd(C
2
H
3
SO
4
)
3
9H
2
O
metals
29
What magnetic moment a metal should have?
Hunds rule
incorporate coupling of magnetic moment to determine
the magnetic state
(1)Maximize S subject to the Pauli exclusion principle
m
s
=1/2 put spins (in different states) parallel

=
s
m
(2)Maximize L subject to the Pauli exclusion principle
m

= -, -+1, , -1, fill higher m

state preferentially

=

m
(3)
J = L-S, L-S+1, , L+S-1, L+S allowed values
Whether it is a minimum or maximum in the ground state
depends on filling function.

=
full half than more is shell when S L
full half than less is shell when S L
J
30
Magnetic state
J
1 2S
L
+
L : 0, 1, 2, 3, 4
S, P, D, F, G
Examples
(1)Full shells : L=0, S=0, and hence, J =0
(2) Half filled shells : L=0 and S=(2+1)(1/2)
3
2
1
0
-1
-2
-3
L=0 and S=7/2
J =L+S=7/2
Eg. Gd
3+
4f
7
5S
2
5P
6
(n=4,=3)
7/2
8
S State
31
3
2
1
0
-1
-2
-3
L=3 and S=1/2
J =L-S=5/2
Eg. Cs
3+
4f
1
5S
2
5P
6
(n=4, =3)
5/2
2
F State
3
2
1
0
-1
-2
-3
L=5 and S=1
J =L-S=4
Eg. Pr
3+
4f
2
5S
2
5P
6
(n=4, =3)
4
3
H State
3
2
1
0
-1
-2
-3
L=5 and S=5/2
J =L+S=15/2
Eg. Dy
3+
4f
9
5S
2
5P
6
(n=4, =3)
15/2
6
H State
32
Rare earth ions
1) J(J g p + = For Sm
3+
and Eu
3+
, there are discrepancies between
experimental p and theoretically calculated value.
High states of the L-S multiplet.
33
Quenching of the orbital angular momentum : Iron group ions
1) S(S 2 p + = Effective number of Bohr magneton 1) J(J g p + =
In the iron group ions the 3d shell, the outermost shell, is responsible
for the paramagnetism and experiences the intense inhomogeneous
electric field produced by neighboring ions.
called the crystal field
breaking L-S coupling (J is meaningless)
splitting 2L+1 sublevels (diminishing the
contribution of orbital motion to magnetic moment)
34
An atom w/. L=1 is placed in the uniaxial crystalline electric field of
two positive ions along the z-axis.
Take S=0 to simplify the problem.
(

2
y x
f(r) ) ( (r)Y R
z f(r) ) ( (r)Y R
2
y x
f(r) ) ( (r)Y R
1 1
10
11
i
i
n
n
n

In a free atom, a single electron in a p-state.

Three degenerate p states
35
In a crystal of orthorhombic symmetry the charges on neighboring
ions will produce an electrostatic potential about the nucleus,
2 2 2
B)z (A By Ax e + + =
Reconstructing unperturbed ground state
zf(r) U yf(r), U xf(r), U
z y x
= = =
+ perturbed term e
0 U U U U U U
x z z y y x
= = = e e e
) I A(I
]dxdydz y Ax [Ax f(r)
]dxdydz B)z (A By [Ax x f(r) U U
2 1
2 2 4
2
2 2 2 2
2
x x
=
=
+ + =

e
Non-diagonal elements
Diagonal elements
36
) I B(I
]dxdydz z By [By f(r)
]dxdydz B)z (A By [Ax y f(r) U U
2 1
2 2 4
2
2 2 2 2
2
y y
=
=
+ + =

e
) I B)(I (A
]dxdydz z z B)[y (A f(r)
]dxdydz B)z (A By [Ax z f(r) U U
1 2
4 2 2
2
2 2 2 2
2
z z
+ =
+ =
+ + =

e
The orbital moment of each of the states
0 U L U U L U U L U
z z z y z y x z x
= = =
Crystal field splits the original degenerate states into non-magnetic states
separated by energies >> H.
quenching of the orbital angular momentum
37
Paramagnetic susceptibility of conduction electrons
Conduction electrons are not bound to atoms so that they are not
included in atomic magnetization.
Each electron has =
B
.
Curie-type paramagnetic contribution (electron spins align w/. H)
Pauli pointed out that only electrons near E
F
(k
B
T) can flip over.
T k
H n
M
B
2
B

= where n is #of conduction electrons

This requires each electron spin align w/. H, independent of all others.
Fermi-Dirac distribution
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1

f
(

,
T
)
T=0
T0

F
k
B
T

F
H=0 H0
38
Fraction of electron participating
F F
B
T
T T k
=

F B
2
B
B
2
B
F
T k
H n
T k
H
T
T
n M

=
|
|
.
|

\
|
|
|
.
|

\
|
=
independent of temperature
2H
DOS
DOS
Consider the density of states D() in the presence of H
Spin electrons lowered in energy by H in H
Spin electrons raised in energy by H in H
H

F

H
flip spins

39
( ) H
T 2k
3N
H
2
3N
H ) ( D M
2
F B
2
F
F

= = = =

N N
Pauli spin magnetization
independent of temperature
The concentration of electrons w/. magnetic moment parallel to H
The concentration of electrons w/. magnetic moment antiparallel to H
H,
T=0K
H ) ( D
2
1
) ( D d
2
1
) H ( D d
2
1
F
0 H
F F

+ + =

N
H ) ( D
2
1
) ( D d
2
1
) H ( D d
2
1
F
0 H
F F

=

N
valid when k
B
T<<
F
40
References :
Kittel, Introduction to Solid State Physics, 8th Ed., Ch.11-12, 2005.
Aschroft and Mermin, Solid State Physics, Harcourt, Ch.31-33, 1976.
Mattis, Theory of Magnetism, Springer, 1985.
Cullity, Introduction to Magnetic Materials, Addison-Wesley, 1972.
Comstock, Introduction to Magnetism and Magnetic Recording,
Wiley-Interscience, 1999.
Spin-dependent Transport in Magnetic Nanostructures, Edited by
Maekawa and Shinjo, Taylor & Francis, 2002.
41
Cooling by isentropic demagnetization
Entropy : A measure of the disorder of a system
The greater the disorder, the higher is the entropy. In the magnetic field
the moments will be partly lined up (partly ordered), so that the entropy
is lowered by the field.
The entropy is lowered if the temperature is lowered, as more of the
moments line up.
When the material is demagnetized at constant entropy, entropy can
flow from the system of lattice vibrations into the spin system.
Z ln k S
B
=
where Z is the partition function

=
=
|
|
.
|

\
|
=
I m
-I m
N
B
M
T k
exp Z

42
Entropy for a spin system depends only for the population distribution.
ab : the system is magnetized isothermally.
bc : the magnetic field is turned off adiabatically.
B/T
|
.
|

\
|
=

H
H
T T
i f
where H

is the effective field

If we start at H=5T and T
i
=10mK
5 . 0
T k
H
B

T
f
~10
-7
K
The first nuclear cooling was done on Cu, T
i
=20mK T
f
~1.210
-6
K
a
b
c
43
|
.
|

\
|
=
B
3.1
T T
i f
Cu nuclei in the metal
where B

=3.1Oe.
The present record for a
spin temperature is about
280pK.
PRL70, 2818 (1993).
Rd
1.2 K