1

X.

PARAMAGNETISM AND DIAMAGNETISM

A. Macroscopic description

Gauss Law for magnetostatics says that the sources of

magnetic induction B are magnetic dipoles, not monopoles:

BdA = 0, div B = 0
(1)
In vacuum, B = 0 H, where 0 = 4 107 Vs/A is the
permeability of vacuum. In matter:

Orbital angular momentum of a hydrogen

atom is described
by a quantum number l and its value is  l(l + 1), with l running from 0 to (n 1), where n is the principal quantum number. The corresponding magnetic moment has a magnitude:


e
e l(l + 1)
= B l(l + 1), B =
|| =
2me
2me
where B = 9.27 1024 J/T is the Bohr magneton. This
magnetic moment precesses about the direction of an applied
field B0 . The projection of on B 0 is quantized with magnetic quantum number ml = l, ..., 0, ..., l (2l + 1 values):
l = ml B

B = 0 (H + M) = B0 + 0 M,
where B0 = 0 H can be regarded as external field and M is
the macroscopic magnetization, i.e. the density of magnetic
dipole moments :
M=

In many (but not all!) cases, there exists linear relation between the external field and magnetization:
0 M = B0 ,
where is magnetic susceptibility. If < 0, the solid is
diamagnetic, if > 0 - paramagnetic. Sometimes magnetic
properties are described by the relative permeability = 1 +
(not to be confused with the magnetic moment ):

Similar arguments apply to the electron spin s = 1/2, with

two possible projections m s = 1/2.
To discuss more complex atoms, one notices that filled
shells have zero total orbital momentum since the components
parallel and anti-parallel to B 0 are equally strong. The same is
true for the total spin magnetic moment because the number
of electrons with spin up and spin down are equal. The total
angular momentum
J is described by quantum number J and

has a value  J(J + 1). The associated magnetic moment has

a magnitude:


|| =  J(J + 1) = gB J(J + 1),
where is the gyromagnetic ratio and g is the Lande gfactor. The projection of on B 0 is quantized with magnetic
quantum number m J = J, ..., 0, ...J (2J + 1 values):
J = gm J B ,

B = 0 (1 + )B0 = 0 B0
For an electron spin:
Like for an electric dipole in an electric field, the potential
energy of a magnetic moment in a field B 0 is given by:
U = B0






e2
+ O(2 ) = 2.0023  2 =
 137
g0 = 2 1 +
2
c
For a free atom the g factor is given by Lande equation:

Potential energy of a solid of volume V in an external field B 0 :

B0
U = V
0

M dB0 = V

B0

g=1+
B0 dB0 = V

2
B
20 0

For paramagnetic, U < 0, and such solids experience attractive force towards locations of higher fields (e.g., attracted to
either pole of permanent magnet). For diamagnetic, U > 0
and they are expelled from regions of high magnetic fields.

B. Magnetic eects in atoms

Magnetic moment of a free atom has three principal

sources: (1) electron spin, (2) electron orbital angular momentum, (3) the change in the orbital magnetic moment induced
by applied magnetic field. (1) and (2) lead to paramagnetism,
while (3) results in diamagnetism.

J(J + 1) + S (S + 1) L(L + 1)
2J(J + 1)
C. Hunds rules

The total angular momentum of electrons J can be calculated as a vector sum of the spin S and orbital L moments,
J = L + S. For light atoms (weak spin-orbit coupling), these
are independent and the so-called L S coupling scheme can
be applied:


L=
ml , S =
ms
Note that for filled shells L = S = 0. The actual calculation
procedure is given by Hunds riles:
1. S is maximized (but consistent with the Pauli principle). This rule is usually explained using the eect

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similar to the exchange interaction. Recall that with
parallel spins, electron wave function of a hydrogen
molecule has to be antisymmetric, which keeps electrons away from each other reducing Coulomb interaction and thus the energy of the electron system. However accurate quantum-mechanical calculations (starting in the 1970s) have shown that the true reason is that
the electrons in singly occupied orbitals are less eectively screened from the nucleus, so that such orbitals
contract and electron-nuclear attraction energy becomes
greater in magnitude (or decreases algebraically).
2. For a given S , m l are such that L is maximized. This
rule has no simple interpretation but it relates to the fact
that the energy is lower when all electrons spin round
the nucleus in the same direction. One can think about
this as follows. Electrons orbiting in one direction have
less chance to meet with each other and on average their
Coulomb energy is reduced.
3. In the ground state J = L S (less than half full shell),
J = L + S (more than half full shell), L = 0, J = S (half
full shell). This rule is related to spin-orbit coupling: for
a single electron the energy is the lowest when the spin
is antiparallel to the orbital angular momentum. However, once the shell is more than half full, the lowest
energy state should have the spin parallel to the orbit.
Example. Cr3+ has configuration of [Ar]3d 3. d shell can take
10 electrons, so it will be less than half full. First rule: S =
3/2. For d shell, l = 2, and m l = 2, 1, 0, 1, 2. Second rule:
L = 0 + 1 + 2 = 3. Third rule: J = L S = 3 3/2 = 3/2 and
m J = 3/2, 1/2, 1/2, 3/2. The Lande g-factor is:
15 24
6
3/2 5/2 + 3/2 5/2 3 4
=1+
=
g=1+
2 3/2 5/2
15
15
D. Curie paramagnetism

The magnetic energy levels in a magnetic field B 0 are

equally spaced:
U = B0 = J B0 = gB B0 m J , m J = J, ..., 0, ...J
With  = gB B0 the partition function is given by:
Z=

emJ /

m J =J

The average magnetic moment is:

C  =

J
1
gB m J emJ /
Z m =J

1/2, i.e. with only two energy levels (we assume g = 2) The
occupancies of these levels are:
f =

eB0 /
eB0 /
, f = B /
B
/
+e 0
e 0 + eB0 /

eB0 /

Magnetization is given by:

M=

1
1
N
(N N ) = N( f f ) =
tanh(B0 /)
V
V
V

At B0 , tanh(B0 /)  B0 / and
M  (N/V)(B0 /) = N2 B0 /V = N0 2 /V = C/
At  B0 , tanh(B0 /)  1 and M  (N/V) = M0 .
For arbitrary J, the system has 2J + 1 equally spaced levels and the magnetization is given by (we do not attempt the
calculation here):
M = (N/V)gJB B j (x), x = gJB B0 /
where B j (x) is known as Brillouin function given by:



x
(2J + 1)x
2J + 1
1
B j (x) =
coth
coth

2J
2J
2J
2J
At high temperatures x  1
coth x =

1 x x3
+
+ ...
x 3 45

and
2J
1 2J 1 1
2J + 1

= =0
2J (2J + 1)x 2J x
x x
2
1 x J+1
(2J + 1) x

=
x

3J
(2J)2 3 (2J)2 3

B(0)

j
B(1)
j

and magnetization becomes:

M

N
J + 1 gJB B0 N J(J + 1)g2 2B
gJB
=
B0
V
3J

3V

The susceptibility is then given by Curie law:



N p2 0 2B C
N J(J + 1)g2 0 2B
=
=
,
3V
3V


where p g j(J + 1) is the eective number of Bohr magnetons and C is known as the Curie constant.

and the magnetization is then found as M = (N/V) C .

For a single electron, with no orbital moment m J = 1/2,
g = 2 and U = B B0 . This is a two-level (binary) system.
Let us first consider N atoms with total magnetic moment J =

E.

Pauli paramagnetism

Non-interacting Fermi gas of lectrons (spin s = 1/2, magnetic moment = B ) also exhibits paramagnetic behavior.

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At B B0  F (which is always the case), the number of spindown (spin-up) electrons is given by N (N ):
N

1
=
2
1
=
2

F
B B0
F

+B B0

1
dD( + B B0 ) 
2

F

1
dD() + B B0 D(F )
2

1
dD( B B0 ) 
2

F

With 0 = 0, we have a two-level system with B 0 and +

B0 , where = 2B0|s|z |0|2 /. The magnetic moment is:

1
dD() B B0 D(F )
2

(2)

 =

At high temperatures, B 0 , Z  2 and:



 
+ B0

1

B0
+ ... 1
+ ... 

 
1+
2

2
which is, in fact, independent on :

The dierence between spin-down and spin-up electrons is:

0 M
1 B (N N )
1
=
=
= 0 2B D(F )
B0
V
B0
V
In 3D, D( F ) = 3N/2F , and
=

For N such molecules in volume V:

=

0 M
1 N N0 |s|z |0|2 Cvv
= 0
=
=
,
B0
V B0
V

which is similar to Curie paramagnetism. At low temperatures,  , the population is nearly all in the ground state:

3N0 2B
2VF

 

Since, usually   F , Pauli susceptibility is much smaller

than Curie susceptibility. The weakness of the eect is a direct consequence of Fermi statistics (similar to electron heat
capacity); only electrons at the Fermi surface ( N B B0 /F )
can contribute. The estimate can be obtained as follows:
N0 2B

0 M 0 N(B B0 /F ) B

=
B0
V
B0
VF

2B0|s|z |0|2
B0 |s|z |0|2
B0

 

N N  D(F )  D(F )B B0 ,
where D(F ) is the density of states at the Fermi energy. The
Pauli susceptibility is then given by:

eB0 / e(+B0 )/
eB0 / + e(+B0 )/

2B0|s|z |0|2
eB0 / 0
B0
==
B
/
0

e
+0

For N such molecules in volume V:

=

0 M
1 N 2N0 |s|z |0|2
= 0
=
B0
V B0
V

This contribution is temperature independent and is known as

Van Vleck paramagnetism.
G. Diamagnetism

F. Van Vleck Paramagnetism

Consider a system with zero magnetic moment in the

ground state, i.e 0| z |0 = 0. Suppose that there exists a nondiagonal matrix element s| z |0  0 of the magnetic moment
operator connecting the ground state with the excited state s
with energy  s = 0 + above the ground state. In weak magnetic field (magnetic energy  ), the first order perturbation
theory gives:
s|z |0B0
|s

0|z |sB0
|s  = |s
|0

In electrostatics, the electric field E(r) can be generated

from the electrostatic potential (r) as E(r) = (r). Since
magnetic monopoles do not exist, it is impossible to introduce
a scalar potential for the magnetic field, but one can define a
vector potential:
B = curl A = A
If r = (x, y, z) and B0 = (0, 0, B0) one can chose
1
A = r B0
2

|0  = |0 +

Now, the ground state 0  has a moment:

s|z |0B0
0|z |s

2B0|s|z |0|2
0|z |sB0
s|z |0 + ... 

0 |z |0  = 0|z |0 +

and the upper state s  has a moment:

s |z |s  

2B0|s|z |0|2
=

Indeed
1
1
1
(rB0 ) = [(B0 )r B0 ( r)] = (B0 3B0 ) = B0
2
2
2
Introduction of A greatly simplifies coupling of external magnetic field into the Schrodinger equation: one only needs to
replace the momentum operator p = i with p qA. For
electrons, q = e and the kinetic energy part of the Hamiltonian becomes:
2
1

e
Hkin =
p r B0
2me
2

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The cross term is:

The susceptibility can be estimated as:

ep (r B0 ) = ep (B0 r) = eB0 (r p)
= 0

and
Hkin =



1
e2
p2 + eB0 (r p) + (r B0 )2
2me
4

0 ZNe2 2
M
1 N
= 0
=
r
B0
V B0
6Vme a

H. Diamagnetism of free electrons

or
Hkin =

p2
e
e2 2 2
+
B0 (r p)z +
B (x + y2 )
2me 2me
8me 0

The second and third terms represent perturbations due to

magnetic field. The energy change is given by:
 =

e2 2
e
B0 |lz | +
B |(x2 + y2 )| = p + d
2me
8me 0

Here, the first term gives paramagnetism, caused by orbital

angular momentum which is already present (no spin appears
in non-relativistic Schrodinger equation). The second term,
represents diamagnetism. We can calculate the induced magnetic moment as:
e2

d =
B0 |(x2 + y2 )|
=
B0
4me
For spherically symmetric distribution, we can estimate
|(x2 + y2 )|  (2/3)|r 2 | = 2ra2 /3 and obtain for atom
with Z electrons:
=

Ze2
B0 ra2 B0
6me

Without any derivation we will state that diamagnetism of

free electrons is given by:
 2
me
1
2
= 0 B D(F )
3V
m
In 3D, D( F ) = 3N/2F , and
=

 
N0 2B me 2
2VF m

For free electrons m = me , and diamagnetic contribution is

3 times smaller than paramagnetic by absolute value; the free
electron gas is paramagnetic with susceptibility:

N0 2B
VF