Summer Internship Project 2019

Report

Study of Magnetic Behavior

and
Magnetic Structure

Submitted by

Suraj Kumar Patel

1st year Int. Msc
NISER, Bhubaneswar

Under the guidance of

Dr. Saptarshi Mandal

Reader F
Institute of Physics
Bhubaneswar

Signature of the Supervisor

 NATIONAL INSTITUTE OF SCIENCE
EDUCATION AND RESEARCH

Certificate
This is to certify that Suraj Kumar Patel , who is currently
pursuing an Integrated M.Sc. course at NISER Bhubaneswar,
undertook a summer project/internship on the topic ”Study of
Magnetic Behavior and Magnetic Structure ”under the guidance
of Dr. Saptarshi Mandal of Institute of Physics Bhubaneswar,
and satisfactorily completed all the requirements for the same.

Dr. Saptarshi Mandal

Reader F
Institute of Physics
Bhubaneswar

i
Contents

1 Classical Mechanics 1
1.1 Lagrangian Formalism . . . . . . . . . . . . . . . 1
1.1.1 Advantages of the Lagrangian approach . . 1
1.2 Hamiltonian Formalism . . . . . . . . . . . . . . . 2
1.2.1 Interpretation of the Hamiltonian . . . . . 3
1.2.2 Advantages of the Hamiltonian formalism 4

2 Quantum Mechanics 5
2.1 Linear Vector Space . . . . . . . . . . . . . . . . . 5
2.2 Dirac Notation . . . . . . . . . . . . . . . . . . . 6
2.3 Operator . . . . . . . . . . . . . . . . . . . . . . . 9
2.4 Eigenvalues and Eigenvectors . . . . . . . . . . . 10
2.5 Basics of Quantum Mechanics . . . . . . . . . . . 10

3 Diamagnetism and Paramagnetism 14

3.1 Magnetization Density and Susceptibility . . . . . 14
3.2 Calculation of Atomic Susceptibility . . . . . . . . 15
3.3 Larmor Diamagnetism . . . . . . . . . . . . . . . 18
3.4 Hund’s Rules . . . . . . . . . . . . . . . . . . . . 19
3.4.1 Russel-Saunders Coupling . . . . . . . . . 19
3.4.2 Hund’s First Rule . . . . . . . . . . . . . . 19
3.4.3 Hund’s second Rule . . . . . . . . . . . . . 20
3.4.4 Hund’s third Rule . . . . . . . . . . . . . . 20
3.5 Paramagnetism . . . . . . . . . . . . . . . . . . . 21
3.6 Curie’s Law . . . . . . . . . . . . . . . . . . . . . 23

ii
 3.6.1 Curie’s Law in solids . . . . . . . . . . . . 24
3.7 Adiabatic Demagnetization . . . . . . . . . . . . . 25
3.8 Pauli Paramagnetism . . . . . . . . . . . . . . . . 26
3.9 Conduction electron diamagnetism . . . . . . . . 28
3.10 Measurement of Pauli Paramagnetism by nuclear
magnetic resonance . . . . . . . . . . . . . . . . . 29

4 Electron’s interaction and Magnetic structure 30

4.1 Estimate of Magnetic Dipolar Interaction energy . 30
4.2 Magnetic Properties of two electron System . . . 31
4.3 Calculation of singlet-triplet splitting . . . . . . . 32
4.4 Spin Hamiltonian And Heisenberg Model . . . . . 35
4.5 Direct Exchange ,Super Exchange,Indirect Exchange,Itinerant
Exchange . . . . . . . . . . . . . . . . . . . . . . 37
4.6 Magnetic interaction in free electron gas . . . . . 38
4.7 Hubbard Model . . . . . . . . . . . . . . . . . . . 40
4.8 Localized Moment in Alloy . . . . . . . . . . . . . 40
4.9 The Kondo theory of resistance minimum . . . . . 41

iii
Chapter 1

Classical Mechanics

1.1 Lagrangian Formalism

In Lagrangian formalism L is a function of q,q̇,t and the Euler
Lagrangian equation is:

∂L d ∂L
− =0 (1.1)
∂q dt ∂ q̇
The above equation is a second order differential equation and
we have to solve n number of differential equation.

1.1.1 Advantages of the Lagrangian approach

. First of all, the Lagrangian is a scalar and is, therefore , much
easier to handle, in general, than vectors and tensors. Second,
the Lagrangian gives rise to equations of motion which have the
same form independent of the coordinate system being used. In
terms of generalized coordinates q i and q̇ i = 1,2, · · · n, we can
write L =L(q i , q̇ i ) and the Euler-Lagrange equations take the
forms
∂L d ∂L
= (1.2)
∂q dt ∂ q̇
In the Lagrangian approach it is also easy to recognize quantities
that are conserved. For example, if the Lagrangian is indepen-

1
dent of a particular coordinate, then we say that the correspond-
ing coordinate is a cyclic variable and the momentum conjugate
to such a variable is conserved.
∂L d ∂L dpi
= = (1.3)
∂q i dt ∂ q˙i dt

1.2 Hamiltonian Formalism

The Lagrangian is a function of the coordinates and the veloci-
ties, which are considered to be independent variables

L ≡ L(q i , q˙i ) (1.4)

The conjugate momenta

∂L
pi = (1.5)
∂ q˙i
and the dynamical equations given by the Euler-Lagrange
equation
∂L d ∂L dpi
= = (1.6)
∂q i dt ∂ q˙i dt
Given these, we can define another fundamental quantity called
the Hamiltonian, which is a function of the coordinates and the
momenta as

pi q˙i − L(q i , q˙i )

X
H ≡ H(q i , pi ) = (1.7)
i

Here q i andpi H are independent variables and q˙i become derived

function of q’s and p’s. Such a transformation is known as a
Legendre transformation. It follows
∂H
= q˙j (1.8)
∂pj

2
 ∂H ∂L
= − (1.9)
∂q j ∂q j
Using the Euler-Lagrange equations becomes
∂H ∂L
= − = −p˙j (1.10)
∂q j ∂q˙j

Equation of motion in the Hamiltonian formalism, take the

forms
∂H ∂H
= q˙i , = −ṗi (1.11)
∂pi ∂q i
which are known as the Hamiltonian equations of motion. n
second order Euler-Lagrange equations in the Lagrange formal-
ism have become 2n first order equations in the Hamiltonian.

1.2.1 Interpretation of the Hamiltonian

In the absence of non conservative forces, the Lagrangian, in the
Cartesian coordinates form
1
L = T − V = m(ẋi )2 − V (xi ) (1.12)
2
The conjugate momenta coincide with the actual momenta in
this coordinate system,
∂L
pi = = mẋi (1.13)
∂ ẋi
In this case,

X X 1
H= pi ẋi − L = ( m(ẋi )2 + V (xi )) (1.14)
i i
2
X p2
= ( i + V (xi )) = T + V = E (1.15)
i
2m
Thus, the Hamiltonian corresponds to the total energy of the
system in the absence of non-conservative forces.

3
1.2.2 Advantages of the Hamiltonian formalism
a) Hamiltonian equations of motion are first order equations
and are, therefore, sometimes easier to handle.

b) The equations are symmetric in q i and pi . This is very useful

when cyclic coordinates are present.In Lagrangian descrip-
tion when a cyclic coordinate is present, the corresponding
conjugate momentum is a constant of motion. This contin-
ues to hold in the Hamiltonian formalism as well, since
∂H
= −ṗi = 0 (1.16)
∂q i
In the presence of even a cyclic coordinate q i , the La-
grangian is a function of the corresponding velocity q˙i and
therefore, we still have to solve n-equations. On the other
hand in the Hamiltonian formalism if q i is cyclic, pi is a
constant and, therefore,

H ≡ H(q 1 · · · ,i−1 , q i+1 · · · q n , p1, · · · pi−1 , α, pi+1 , · · · , pn )

(1.17)
Consequently, the number of equations we have to solve is
reduced.
c) It is easier to recognize other conserved quantities in the
Hamiltonian formalism.

4
Chapter 2

Quantum Mechanics

2.1 Linear Vector Space

A set of quantities {Vi }, with a definite rule for addition and
multiplication by scalars, is called a set of vectors if they satisfy
1. Vi + Vj = Vj + Vi ,(commutative law of addition)
2. Vi + (Vj + Vk ) = (Vi + Vj ) + Vk (associative law of addition),
3. α(Vi + Vj ) = αVi + αVj ,
4. (α + β)Vi αVi + βVi , (distributive law),
5. (αβ)Vi = α(βVi ), (associative law of multiplication).
If V represents the set of vectors {Vi }(namely, Vi ∈ V ) such
that
1. αVi + βVi ∈ V. where α, β are constants,
2. there exists a unique null vector ∅∈ V such that
Vi + ∅ = Vi = ∅ + Vi
3. corresponding to every vector Vi ∈ V, there exists a unique
inverse (−Vi ) ∈ V such that
Vi + (−Vi ) = ∅

5
 4. 0.Vi = ∅
5. 1.Vi = Vi
then, V is called linear vector space.

2.2 Dirac Notation

Arbitrarily vector in Vn , with an inner product, can be ex-
pressed uniquely in terms of an orthonormal basis {ei } as
n
X
V = v i ei (2.1)
i=1

We can collect the n-tuple into a column matrix and then the
correspondence  
v1
v 
 2
V =  ..  (2.2)
.
vn
Basis, in this case, is chosen such that
 
0
0 
 
 .. 
.
ei =   (2.3)
1 
 
0 
0
where the non-zero entry is in the i-th row and
n
X
V = vi ei (2.4)
i=1

With such a representation of a vector, addition of vectors and

multiplication of a vector by scalar obey matrix formulae.

6
Matrices satisfy all the properties of vectors and can, therefore,
provide a representation for them.A column representation of a
vector is called a ket vector and is denoted by the correspondence
representation for them
 
v1
v 
 2
ket V ≡| V i =  ..  (2.5)
.
vn
However, given a column vector, we can also take its Hermi-
tian conjugate to obtain a row vector as
 †  ∗ T
v1 v1
v  v 
 2  2
 ..  =  ..  = (v1∗ v2∗ · · · vn∗ ) (2.6)
. .
vn vn
This can also provide a representation for V. It is called bra
vector and is denoted by
bra V ≡ hV |=| V i† = (ket V )† = (v1∗ v2∗ · · · vn∗ ) (2.7)
Corresponding to a ket vector there exist a unique bra vector
and vice versa. product of a bra vector with a ket vector, using
the matrix laws of multiplication
n
X
hW | V i = V = wi∗ vi = (W, V ) (2.8)
i=1

Which is the inner product of W with V. Since

n
X
V = vi ei (2.9)
i=1

where the components vi are numbers and ei ’s are the basis

vectors we can also define basis ket vectors as (the non-zero

7
element is in the i-th row)
 
0
 ... 
 
1 
 
| ei i =   ≡| ii (2.10)
0 
.
 .. 
0
and the basis bra vectors as
hei |=|i† (0 0 · · · 1 0 0 · · · 0) ≡ hi | (2.11)
With these, we can write
n
X n
X
|Vi= vi | ei i, hV |= vi∗ hei | (2.12)
i=1 i=1

which leads to n
X
hW | V i = wi∗ vi (2.13)
i=1
This implies that
hei | ej i = δij (2.14)
which is the orthonormality relation for the basis vectors in the
Dirac notation. if n
X
|Vi= vi | ei i (2.15)
i=1
then, using (2.14)
n
X n
X
hei | V i = vj hei | ej i = vj δij = vi (2.16)
j=1 j=1

The components of a ket vector, in a given orthonormal basis,

can be obtained by taking the inner product of the vector with
the appropriate bra basis vector.

8
2.3 Operator
An operator is a map of a vector into another vector.
Ω
→| V 0 i
|Vi− or Ω | V i =| ΩV i =| V 0 i (2.17)
operator Ωacting on the vector| V i transforms it to the vector
| V 0 i. Operators can also act on bra vectors to produce other
bra vectors. However, an operator cannot act on a ket vector to
give a bra vector and vice versa.

The simplest linear operator is the identity operator,1, which

leaves all vectors invariant. Namely,
1 | V i =| V i, hV | 1 = hV | (2.18)
since our ket and bra vectors are column and row matrices
respectively, a matrix representation of operators would involve
square matrices with n2 elements, in general.
Ω0 Ω | V i =
6 ΩΩ0 | V i (2.19)
When two or more operator acts on a vector,the order in which
they act is important.
Ω0 Ω − ΩΩ0 = [Ω0 , Ω] (2.20)
is called the commutator ofΩ0 and Ω and is generally nonzero.
When it vanishes operator commute.

We can also define the inverse Ω−1 of an operator Ω such that

the action of Ω on any arbitrary vector followed by the inverse
(or vice versa) leaves the vector unchanged.
Ω−1 Ω | V i =| V i = ΩΩ−1 | V i (2.21)
implies that
Ω−1 Ω = ΩΩ−1 ≡ 1 (2.22)

9
2.4 Eigenvalues and Eigenvectors
An operator acting on a particular vector takes it to a new vector

Ω | V i =| V 0 i (2.23)

However, if the effect of an operator acting on a particular

vector is to simply multiply it by a constant (scalar), i. e.,

Ω|Vi=ω |Vi (ω is a scalar ) (2.24)

Then we say that| V i is an eigenvector of the operator Ω with

the eigenvalue ω.For linear operators , if| V i is an eigenvector,so
is α | V i where α is a scalar. This arbitrariness can be used to
normalize an eigenvector. (2.24) can also be written as
n
X
(Ωij − ωδij )vj = 0 (2.25)
j=1

This forms a set of linear homogeneous equation, known as the

characteristic equation. A nontrivial solution, in this case, exists
if the determinant of the co efficient matrix vanishes, i.e.,

det(Ωij − ωδij ) = 0 (2.26)

From this equation We would get n solutions for ω, which will

correspond to all the eigenvalues of the operator Ω.

2.5 Basics of Quantum Mechanics

Quantum correspondence principle

From classical Poisson bracket of observable we can deduce that

10
 This shows that the quantum commutator of two operators is
ih̄ times the value of their classical Poisson bracket.For macro-
scopic systems effects of the order of h̄ can be taken to be
negligible, the commutator can neglected and hence the order
of quantities would not matter. Therefore Planck’s constant,
h̄,measures the non-classical nature of systems.That is one re-
covers classical mechanics in the limit h̄ → 0.

Postulates of quantum Mechanics

Laws of classical mechanics need some do modification so that

they can be applied to microscopic systems. These modifica-
tions are implemented in the following way. Given a classical
Hamiltonian system, one goes over to the quantum description
through the following postulates.
1. In classical mechanics a system at a fixed time is described
by the coordinates x(t) and the momenta p(t).

In quantum mechanics the state of a system at a fixed time

is denoted by the infinite dimensional vector | ψ(t)i which
belongs to a Hilbert space.
2. Every dynamical variable w in classical mechanics is a func-
tion of the phase space variables x and p. Thus, ω =ω(x,p ).

In quantum mechanics the observable x and p are the Her-

mitian operators X and P with the nontrivial commutation
relation
[X.P ] = ih̄ = ih̄1. (2.27)
These operators have the following matrix elements in the
eigenbasis of the operator

hx | X | x0 i = xδ(x − x0 ) (2.28)

11
 d
δ(x − x0 )
hx | P | x0 i = −ih̄ (2.29)
dx
Any operator Ω corresponding to the classical observable
ω(x,P )is obtained as the same function of the operators X
and P. Thus,
ω(x, p) → Ω(X, P ) (2.30)

3. In classical mechanics if a system is in the state x(t) and

p(t), then, the measurement of an observable ω(x.p) would
yield a unique value and the system will be unaffected by
the process of measurement.
Quantum mechanics,gives probabilistic results. If a system
is in a state | ψithen a measurement corresponding to Ω
yields one of the eigenvalues, ωi , of Ω, with a probability
| hωi | ψi |2 X
P (ω)i = , P (ωi ) = 1 (2.31)
hψ | ψi i

As a result of the measurement, the state of the system

changes to the eigenstates | ωi i of the operator Ω.
4. In classical mechanics, the state variables change with time
according to Hamilton’s equations of motion In quantum
mechanics, the state vectors evolve with time according to
the Schrodinger equation
d
ih̄ | ψ(t)i = H | ψ(t)i (2.32)
dt
where H = H(X,P) is the Hamiltonian operator.
This postulate is also not an independent postulate.

Expectation Value

Let us suppose that a physical system is in a quantum me-

chanical state | ψi and that a measurement corresponding to

12
the operator Ω is made. Then we will obtain an eigenvalue ωi
with probability P(ωi ).Infinite number of such experiments ob-
tains a variety of values with different probabilities. We can ask
what is the statistical mean of these measurements, which we
can then, identify with the average value of the operator in the
state, namely,
X
hΩi = P (ωi )ωi (2.33)
i
It now follows that

hΩi = hψ | Ω | ψi (2.34)

where we have used the completeness relation of the eigenbasis

of the operator in the intermediate steps, namely,
X
| ωi ihωi |= 1. (2.35)
i

We note that hΩi is known as the expectation value of the op-

erator Ω in the state | ψi and gives the statistical mean of the
measurements performed on the system in that state. It is clear
from (3.34) that if the state is an eigenstates of the operator,
then the expectation value would be eigenvalue corresponding
to that state. We can similarly define the expectation value of
the operator Ω2 that state| ψi.
X
hΩ2 i = P (ωi )ωi2 (2.36)
i

Similarly, we can calculate the expectation value of any higher

power of the operator and these would correspond to the familiar
moments of a distribution in statistical mechanics.

13
Chapter 3

Diamagnetism and
Paramagnetism

3.1 Magnetization Density and Susceptibility

At T=0 magnetization density M(H)

1 ∂E0 (H)
M (H) = − (3.1)
V ∂H
If system is in thermal equilibrium at Temperature T ,then mag-
netization density is thermal equilibrium average of each exited
state of energy En (H):

P − kEnT
n Mn (H)e
B
M (H, T ) = P − kEnT (3.2)
ne
B

WhereMn (H)is
1 ∂E0 (H)
Mn (H) = − (3.3)
V ∂H
In thermodynamics form
1 ∂F
M =− (3.4)
V ∂H

14
Where F (Helmholtz free energy ) is defined by
− k FT
X − En (H)
e B = e kB T (3.5)
n

Susceptibility is defined as
∂M 1 ∂ 2F
χ= =− (3.6)
∂H V ∂H 2
We can measure the magnetization by recording the force ex-
erted on specimen by an in-homogeneous field varying with
time,for change in free energy on moving specimen from x to
x + dx will be
∂F ∂H ∂H
dF = F (H(x + dx)) − F (H(x)) = dx = −V M dx
∂H ∂x ∂x
(3.7)
so force per unit volume is
1 dF ∂H
f =− =M (3.8)
V dx ∂x

3.2 Calculation of Atomic Susceptibility

In the presence of a uniform magnetic field The Hamiltonian of
an ion is modified in:
P p2i
1. In total kinetic energy T0 = 2m ,The momentum of each
electron is replaced by
e
pi → pi + A(ri ) (3.9)
c
where A is vector potential and we take
1
A=− r×H (3.10)
2
so that it satisfies
H = ∇ × A and ∇.A = 0 (3.11)

15
2. The interaction energy of the field with each electron spin
si = 12 σi must be Hamiltonian

X
∆H = g0 µB HSZ , (Sz = siz ) (3.12)
i
where is,Bohr magneton is given by
eh̄
µB = = 0.579 × 10−8 eV /G (3.13)
2mc
g0 ,the electronic g-factor is given by
α e2 1
g0 =2[1 + + O(α2 ) + · · · ], α= ≈
2π h̄c 137
=2.0023 (3.14)

Because of(3.9)total kinetic energy operator must be re-

placed by
1 X e 2 1 X e
T = [pi + A(ri )] = (pi − ri × H)2
2m i c 2m i 2c
(3.15)
Which implies
e2 2
X
T = T0 + µB L.H + 2
H (x2i + yi2 ) (3.16)
8mc i

L is total electronic orbital angular momentum

X
h̄L = ri × pi (3.17)
i
Now the spin term combines with this equation to give A
field dependent Hamiltonian
e2 2
X
∆H = µB (L + g0 S).H + 2
H (x2i + yi2 ) (3.18)
8mc i

16
The energy shift is very small due to which perturbation
theory can be applied.By applying second-order perturba-
tion theory
En → En + ∆En ;
X | hn | ∆H | ni |2
∆En = hn | ∆H | ni + (3.19)
0
En − En0
n 6=n

by inserting (3.18) to (3.19)

X | hn | µB H.(L + g0 S) | ni |2
∆En = µB H.hn | L + g0 S | ni +
0
En − En0
n 6=n
e2 2
X
+ 2
H hn | (x2i + yi2 ) | ni
8mc i
(3.20)
This is very important equation for theory of susceptibility
of individual atoms,ions or molecules.

Unless term linear to H vanishes in 3.20 it will mostly the

dominant term.If it doesn’t vanish, will be of order unity
so that
eh̄H
µB H.hn | L + g0 S | ni = O(µB H) ∼ ∼ h̄ωc (3.21)
mc
This is indeed very small.For determining the size of last
term in H , will be of the order of the square of a typical
atomic dimension,so that
e2 2
X eH 2 2 h̄ωc
2
H hn | (x2i + yi2 ) | ni = O[( ) ma0 ] ≈ (h̄ωc )( 2 )
8mc i
mc e /a 0
(3.22)
This term is smaller than linear term(2.21).The second term
in(3.20) is also smaller than the first by a factor of order
,where is a typical atomic excitation energy.

17
3.3 Larmor Diamagnetism
When we take a solid composed of ions with all electronic shell
filled it has zero spin and orbital momentum in its ground state
| 0i
J | 0i = L | 0i = S | 0i = 0 (3.23)
since the ground sate of a closed shell is spherically symmetrical
only the third term in 3.20 contributes to the field-induced shift
in ground state energy

e2 2
X
2 2 e2 2
X
∆E0 = 2
H h0 | (xi + yi ) | 0i = 2
H h0 | (ri2 ) | 0i
8mc i
12mc
(3.24)
If ( all but very high temperatures case) there is negligible prob-
ability of the ion being in any but its ground state in thermal
equilibrium, the susceptibility of a solid composed of N such ion
is given by
N ∂ 2 ∆E0 e2 N X
χ=− 2
= 2
h0 | (ri2 ) | 0i (3.25)
V ∂H 6mc V
This is known as Larmor Diamagnetic Susceptibility.
The equation(3.25) describe magnetic response pf the solid,noble
gases and simple ionic crystal such as alkali halides,Because of
only small distortion of ion in this crystalline environment. Now
converting this to molar susceptibility χmolar

molar e2 2 e2 2 NA a30
χ = −Zi NA 2
hr i = Zi ( ) h(r/a0 )2 i (3.26)
6mc h̄c 6
where mean square ionic radius is
1 X
hr2 i = h0 | (ri2 ) | 0i (3.27)
Zi

18
 2
e 1
Since a0 = 0.529Ao , hc = 137 and NA = 0.6022 ∗ 102 4

χmolar = −0.79Zi × 10−6 h(r/a0 )2 icm3 /mole (3.28)

As h(r/a0 )2 i is of order unity , M is minute as compared to H.

3.4 Hund’s Rules

If we have a free atom or ion in which all electronic shells are
filled or empty except for one.This one electron level are char-
acterized by orbital angular momentum l.For a given l , lz can
have (2l +1) values and two possible spin.So such a shell will
contain 2(2l +1) one electron level.Let n be the number of elec-
tron in a shell.If the electron did not interact with one another
,The ionic ground state will degenerate.However due to coulomb
interaction and spin orbital interaction that degeneracy will be
lifted.Except for the heaviest ions lowest lying level after the
lifting of degeneracy can be described by simple set of rules.

3.4.1 Russel-Saunders Coupling

The Hamiltonian of an atom or ion can be taken to commute
with the total electronic spin , orbital angular momenta and
total electronic angular momentum j=LS.The state of ion in
terms of quantum numbers are then L, Lz , S, Sz , J, Jz .Which are
eigenstates of operatorsL2 , Lz , S 2 , Sz , J 2 , Jz .

3.4.2 Hund’s First Rule

When placing n electron into the 2(2+1)levels of partially filled
shell the largest total spin is for lowest energy electron.The
largest values of S is equal to Sz .If n ≤ 2+1 all electron can have
parallel spins with different values of lz .Hence,S= 21 n when n ≤
2l +1.When n= 2l +1 S has its maximum value l + 21 .If Electron

19
after the 2l +1)th are required by exclusion principle to have
opposites spin and S is reduced from maximum value by half a
unit.

3.4.3 Hund’s second Rule

The total orbital angular momentum L of the lowest lying sates
has the largest value which is largest magnitude of lz .Thus first
electron in the shell will go into a level with lz equal to its maxi-
mum value l.The second must have have same spin as first(RULE
2).And by exclusion principle it cannot have same lz .It can best
have| lz |= l − 1,leading to total L of 2l -1.If shell is less then half
filled L=l+(l -1)+...+[l -(n-1)],And L= when it is half filled.

3.4.4 Hund’s third Rule

The first two rule determine values of L and S assumed by the
States of the lowest energy.This leaves (2L+1)(2S+1) possible
sates.It is further classified according to their total angular mo-
mentum J, which can have all integral values between | L-S |
L+S .The lifted degeneracy in the set can be represented by A
term in Hamiltonian of the form λ(L.S).Spin orbital coupling
will favor maximum J(parallel orbital and spin angular momen-
tum)if λ is negative,and minimum(anitparallel orbital and spin
angular momentum )if λ is positive.λ is positive for shell that
are less than half filled and negative for more than half filled.So
value J assumes in the lowest state of energy is

J =| L − S |, n ≤ (2l + 1)
J = L + S, n ≥ (2l + 1) (3.29)

When determining lowest lying J-multiplet(term) for ion in

a solid one only encounters only 22 cased:1 to 9 electrons in as
d -shell (l=2) or 1 to 13 in an f -shell (l=3).Ground sate multiplet

20
in these cases are not described by the simple triad SLJ; instead
The angular momentum, is a given by

L = 0 1 2 3 4 5 6
(3.30)
X = S P D F G H I

The spin is specified by affixing 2S+1 (multiplicity)to letter as

a super-fix and J is given as number J, affixed by right sub-
script.So the lowest lying J Multiple is there for described by
symbol: 2S+1 XJ

3.5 Paramagnetism
There are two cases to to distinguish
1. if Shell has J=0 then the ground sate is non-degenerate
and the linear term in energy shift (3.20) vanishes.However
second term may not vanish and the shift in ground date
energy is given by
e2 2
X
2 2
X | h0 | µB H.(L + g0 S) | ni |2
∆E0 = H h0 | (xi + yi ) | 0i −
8mc2 i n
En − E0
(3.31)
And susceptibility becomes
N ∂ 2 ∆E0
χ=−
V ∂H 2
N e2 2
X
2 2
X | h0 | µB H.(L + g0 S) | ni |2
=− [ H h0 | (xi + yi ) | 0i − 2µ ]
V 4mc2 i n
En − E 0
(3.32)

21
 The first term is just Larmor Diamagnetic Susceptibility.The
second term has a opposite sign to the first term .So it
favors alignment of moment parallel to the field, Param-
agnetism.This paramagnetic correction to Larmor diamag-
netic susceptibility is known as Van Vleck Paramagnetism
provided that the free energy is just the ground-state en-
ergy.

2. If the shell does not have J=0 then first term in energy
shift will not vanish,And always be so much larger then
the other that they can be ignored. In which ground state
is (2J+1)-fold degenerate in non zero field and we have to
diagonalize the (2J+1)-dimensional matrix

hJLSJz | (Lz + g0 Sz ) | JLSJz0 i Jz , Jz0 = −J, · · · , J

(3.33)
This task is made simple by Wigner-Eckart theorem.Which
gives

hJLSJz | (Lz + g0 Sz ) | JLSJz0 i = g(JLS)hJLSJz | J | JLSJZ 0 i

(3.34)
Since the matrix elements of Jz are

hJLSJz | JZ | JLSJz0 i = Jz δJZ JZ0 (3.35)

it follows that

hJLSJz | (Lz + g0 Sz ) | JLSJz0 i = g(JLS)Jz δJZ JZ0 (3.36)

The value of g(JLS)(Lande g-factor)is

1 1 L(L + 1) − S(S + 1)
g(JLS) = (g0 + 1) − (g0 − 1)
2 2 J(J + 1)
(3.37)

22
 Taking g-factor g0 to be exactly 2
3 1 S(S + 1) − L(L + 1)
g(JLS) = + [ ] (3.38)
2 2 J(J + 1)
(3.34)is equivalent to
hJLSJz | (Lz + g0 Sz ) | JLSJZ 0 i = hJLSJz | g(JLS)J | JLSJZ 0 i
(3.39)
and without state vectors
Lz + g0 Sz = g(JLS)J (3.40)
If the splitting between the zero field atomic ground state
multiplet and first excited multiplet is large compared to
kB T,then(3.40) permits to interpret first term in (3.20) as
expressing the interaction (-µ.H) of the field with a mag-
netic moment that is proportional to total angular momen-
tum of the ion,

µ = −g(JLS)µB J (3.41)

3.6 Curie’s Law

If only lowest 2J+1 states are thermally excited with appreciable
probability,the the free energy is:
J
−βF
X 1
e e−βγHJz , γ = g(JLS)µB , β = (3.42)
kB T
Jz =−J
using Brillouin function we can get:
N (gµB )2 J(J + 1)
χ= , kB T >> gµB H (3.43)
V 3 kB T
This variation of susceptibility inversely with the temperature
is known as Curie’s law.It characterizes paramagnetic system
with perfect moment whose alignment is favored by the field
and opposed by the thermal disorder.

23
3.6.1 Curie’s Law in solids
For crystal containing rare earth metal we can write the curie’s
law as

1 N µ2B p2
χ= (3.44)
3 V kB T
where, p,”Effective Bohr magneton number” is given by

1
p = g(JLS)[J(J + 1)] 2 (3.45)
In case of exception like samarium and europium the J-multiplet
lying just above the ground state is so close in energy that (a)the
energy denominator in second term in 3.20 are small enough to
be important(b)the probability of some ions being thermally ex-
cited out of state of lowest j is appreciable.

The transition metal from iron group obeys curie’s law but
get its p from(3.45) only if S is given by Hund’s rule,L is zero
and J is equal to S.This phenomenon is know as quenching of or-
bital angular momentum,and in particular example crystal field
splitting.

Crystal field splitting is unimportant for rare earth ion. But

in case of transition metal ions the partially d-shell are the outer-
most electronic shell and strongly influenced by their crystalline
environment.The electron in partially filled d-Shell are subject
to non negligible electric fields that do not have spherical sym-
metry,but only symmetry of the crystalline site at which the ion
is located.

We have to modify Hund’s third rule as we are not doing addi-

tional perturbation om (2S+1)(2L+1)-fold set of states. In case

24
of iron group the crystal field id very much large then the spin-
orbit coupling,so we can ignore spin-orbit coupling perturbation
complete.And since crystal field perturbation depends only on
spatial variable it will not split spin degeneracy,but can lift the
degeneracy of orbital L multiplet if it is sufficiently asymmetric.

3.7 Adiabatic Demagnetization

Helmholtz free energy is F= U - TS,where U in internal energy
and entropy is given S(H,T) is given by

∂F 1
S = kB β 2 , β= (3.46)
∂β kB T
From (3.42) we get that βF depends on β and H only through
their product

1
F = Φ(βH) (3.47)
β
So entropy is

S = kB [−Φ(βH) + βHΦ0 (βH)] (3.48)

which depends only on the product.So if we lower the field
acting on a spin system adiabatically the temperature will be
lowered by a proportional amount

Hf inal
Tf inal = Tinitial ( ) (3.49)
Hinitial
This method is used to lower the temperature to a very high
scale.But at very small scale temperature dependence of zero-
field entropy is brought about by the existence of magnetic in-
teraction of paramagnetic ion nd other effect.

25
3.8 Pauli Paramagnetism
For conduction electron magnetism if we neglect the electron
orbital motion responds toward the field(that is electron to have
only a spin magnetic momentum but no charge) then: Each
electron will contribute to magnetization density if its spin is
parallel to field h and if anitparallel. If we take n+− is no of
electron per unit volume with spin parallel(+) or anitparallel(-)
to H,the magnetization density will be

M = −µB (n+ − n− ) (3.50)

Now the only effect of field is shift the energy of each electron
level by µB H.Now let g ± (ε)dε is the number of electrons of
specified spin per unit volume in energy range ε to ε + d.In the
absence of field
1
g± (ε) = g(ε) (H = 0) (3.51)
2
Energy of electronic level with spin parallel to field is shifted up
from zero to µB H,the number level with energy ε in the presence
of H is same as the number with energy ε-µB H. in the absence
of H :

1
g+ (ε) = g(ε − µB H) (3.52)
2
Similarly

1
g− (ε) = g(ε + µB H) (3.53)
2
The number of electron per unit volume for each specific re-
gion is

26
 Z
n± = dεg± (ε)f(ε) (3.54)

where f is the Fermi function

1
f(ε) = (3.55)
eβ(ε−µ) + 1
The vale of µ is determined by total electronic density is given
by

n = n+ + n− (3.56)

Eliminating µthrough this we can find magnetization density as

a function of electron density n.
However, in metals one is very much in degenerate case.As µB H
very small, one can expand density level as

1 1 1
g± (ε) = g(ε ± µB H) = g(ε) ± µB Hg 0 (ε) (3.57)
2 2 2
With(3.54)it gives
Z Z
1 1
n± = g(ε)f(ε)dε ∓ µB H dεg 0 (ε)f(ε) (3.58)
2 2
From (3.56) we get

Z
n= g(ε)f(ε)dε (3.59)

This is the formula in the absence of the field so chemical µ can

be taken to have its zero field value

27
 kB T 2
µ = εF [1 + O( )] (3.60)
εF
now from 3.50 and 3.58 we get
Z
M = µB H g 0 (ε)f(ε)dε
2
(3.61)

At zero temperature

M = µ2B Hg(εF ) (3.62)

This equation is also valid for all but high temperature. Pauli’s
Paramagnetic susceptibility is

χ = µ2B g(εF ) (3.63)

In contrast to curie’s law it is independent of temperature.

The difference between theoretical and measured value by

Pauli susceptibility in case of some alkali metal is a result of
neglected electron-electron interaction.

3.9 Conduction electron diamagnetism

Now we only consider paramagnetic effect arising due to cou-
pling of intrinsic spin and the applied field H.There are also
diamagnetic affect arising from the coupling of the field to the
orbital ,motion of electron.At very low temperature, high fields
and high purities (ωc )there is a complicated oscillatory structure
to the dependence on M on H.in ordinary specimen though the
dependence of M on H doesn’t vanishes out to zero and the non-
vanishing magnetization anitparallel to H is known as Landau

28
Diamagnetism and is due to orbital electronic motion induced
by field.
1
χLandau = − χP auli (3.64)
3

3.10 Measurement of Pauli Paramagnetism

by nuclear magnetic resonance
To calculate electron spin Paramagnetism we need a probe that
is strongly couple with spin magnetic moment then field arises
from electronic transnational motion.The probe is magnetic mo-
ment of the ionic nuclei.
In an applied magnetic field the (2I+1) degenerate spin are split
by an amount γN H.This splitting can be detected by observing
the resonant absorption of energy at angular frequency γN Hh̄ .

29
Chapter 4

Electron’s interaction and

Magnetic structure

1. Magnetic interaction discrete mental arises from their mag-

netic field either directly or indirectly. However the most
important source of magnetic interaction is electron-electron
interaction.

2. Band theory is very necessary to understand non magnetic

properties and magnetic ordering in solid.

4.1 Estimate of Magnetic Dipolar Interaction

energy
The direct dipolar energy of two dipoles separate by r is
1
U= [m1 .m2 − 3(m1 .r̂)(m2 .r̂)] (4.1)
r3
Atomic dipole moment have a magnitude approximately equal
to
(gµB )2 e2 2 a0 3 e2
U≈ ≈( ) ( ) (4.2)
r3 h̄c r a0

30
 Hence size of U becomes .In a magnetic solid moment are very
small and hence is U.now if we can find why electrostatic energy
depends on direction of the moment, then we can tell source
of magnetic moment is important then the dipolar interaction.
Spin-orbit coupling is the major source of magnetic interaction.

4.2 Magnetic Properties of two electron Sys-

tem
To show that Pauli principle can lead to magnetic affect even
when there is are no spin dependent term in Hamiltonian. Since
H does not depends on spin, the general stationary State is
product of orbital stationary State having Schrodinger equation,
h̄2
Hψ = − (521 + 522 )ψ + V (r1 , r2 )ψ = Eψ (4.3)
2m
With any linear combination of four spin state.

|↑↑i, |↑↓i, |↓↑i, |↓↓i (4.4)

We can chose these linear combination to have definite values of

Total spin S and its componentSz along an axis.
STATE S SZ
√1 (|↑↓i− |↓↑i) 0 0
2
|↑↑i 1 1
1
√ (|↑↓i+ |↓↑i)
2
1 0
|↓↓i 1 -1
The state with S=0 (singlet state) changes sign when the spin is
interchanged, while three state with S=1(triplet state) do not.
Total wave function is a product of it’s spin and orbital part,
so solutions to the orbital Schrodinger equation that does not
change sign under interchange of r1 r2 (symmetric) must describe

31
singlet state, while solutions that changes sign(asymmetric)go
with triplet state. So there is strict relation between spatial
symmetry to spin independent Schrodinger equation and total
spin.
If Es and Et are lowest eigenvalues of (4.3) associated to sin-
glet and triplet state then ground state will have either zero
or one spin depending upon which one is greater Es orEt ,and
we approached this solution by considering spin-independent
Schrodinger’s equation.

For two electron system we have elementary theorem which

state that ground state of this system must be asymmetric. Im-
plies it must have zero total spin.

4.3 Calculation of singlet-triplet splitting

The singlet-triplet energy splitting measure the extent to which
anitparallel spin alignment is more favorable than parallel spin.
Since Es anEt are eigenvalue of Hamiltonian containing only elec-
trostatic interaction, so this energy is the dominant source of
magnetic interaction.
If we ignore electron coulomb interaction in V (r1 , r2 ) ,then the
equation (4.3) becomes.

(h1 + h2 )ψ(r1 , r2 ) = Eψ(r1 , r2 ) (4.5)

Where//
h̄2 2 e2 e2
h=− 5i − − , i = 1, 2 (4.6)
2m | ri − R1 | | ri − R2 |
As (4.5) is a sum of one electron Hamiltonian, the solution can
be got from solution of one electron Schrodinger’s equation:

hψ(r) = εψ(r) (4.7)

32
From which symmetric solution of lowest energy to the approx-
imate two-electron Schrodinger equation is:

ψs (r1 , r2 ) = ψ0 (r1 )ψ1 (r2 ), Es = 2ε0 (4.8)

and lowest anti-symmetric solution is

ψs (r1 , r2 ) = ψ0 (r1 )ψ1 (r2 ) − ψ0 (r2 )ψ1 (r1 ), Et = ε0 + ε1

(4.9)
the singlet-triplet splitting is then

Es − Et = ε0 − ε1 (4.10)

This solution to equation is fails to deal with electron- elec-

tron interaction when the proton are very far apart. For well
separated proton solutions to the () are given by tight-binding
method. This method takes one electron stationary State wave
function to be linear combination of atomic stationary State
wave function centers at lattice R.when N=2 the correct linear
combination are

ψ0 (r) = φ1 (r) + φ2 (r),

ψ1 (r) = φ1 (r) − φ2 (r), (4.11)

For two electron system

ψs (r1 , r2 ) = φ1 (r1 )φ2 (r2 ) + φ2 (r1 )φ1 (r2 )+

φ1 (r1 )φ1 (r2 ) + φ2 (r1 )φ2 (r2 ) (4.12)

And

ψt (r1 , r2 ) = 2[φ2 (r1 )φ1 (r2 ) − φ1 (r1 )φ2 (r2 )] (4.13)

33
 (4.12) Gives excellent approximation to the Schrodinger equa-
tion (4.5) in which electron-electron interactions are ignored but
give a very bad approximation to the original Schrodinger equa-
tion (3.3) in which electron-electron interactions are retained.
The first two term electron is localized in orbit in neighborhood
of different nucleus. When protons are far apart this is quite
good. However the last two term is localized in orbit in neigh-
borhood of same nucleus, which describe hydrogen molecule as
H− ion which is inappropriate when electron-electron interac-
tions are allowed.

When we introduce electron-electron interactions into the

Hamiltonian, the triplet will give lower energy than the singlet.
This however does not imply that ground state is a triplet. For
much lower energy than the independent electron ground state,
a symmetric state is given by only taking first two part in (4.12)

ψ̄s (r1 , r2 ) = φ1 (r1 )φ2 (r2 ) + φ2 (r1 )φ1 (r2 ) (4.14)

The theory that takes its approximation to singlet and triplet

ground state of full Hamiltonian (4.3) to be proportional to
(4.14) and (4.13) is known as The Heitler-London approxima-
tion.

Heitler-London singlet state is more accurate for widely sep-

arated proton. But when proton are very close the indepen-
dent electron approximation (4.8) is more accurate. The in-
dependent electron approximation starts with two one-electron
wave function appropriate to a single doubly charged nucleus,
whereas Heitler-London approximation work with one electron
wave function for a singly charged nucleus.

The Heitler-London uses singlet and triplet wave function

34
(4.14) and (4.13) to estimate singlet-triplet splitting as
(ψ̄s , H ψ̄s ) (ψ̄t , H ψ̄t )
Es − Et = − (4.15)
(ψ̄s , ψ̄s ) (ψ̄t , ψ̄t )
In the limit of large spatial separation the equation is

e2 e2
Z
1
(Es − Et ) = dr1 dr2 [φ1 (r1 )φ2 (r2 )]( +
2 | r1 − r2 | | R1 − R2 |
2
e e2
− − )[φ2 (r1 )φ1 (r2 )]
| r1 − R1 | | r2 − R2 |
(4.16)
As this is a matrix element between two sate differ through
exchange of coordinate, the singlet-triplet energy difference is
known as exchange splitting.as atomic orbitalφi (r) is strongly
localized in the neighborhood of r = Ri ,the φ factor ensures
that the singlet-triplet energy splitting will fall off rapidly with
the distance | R1 − R2 | between protons.

4.4 Spin Hamiltonian And Heisenberg Model

The dependence of the spin of two electron system on the singlet-
triplet energy splitting is very important to understand energetic
of the spin configuration of real insulating solids. Where two
protons are very far the ground State describe two independent
hydrogen atom and therefore fourfold degenerate. But when
they brought closer, there is a splitting in the degeneracy due
to interaction between atoms, which is small in compared to
all other excitation energy of two-electron system. Under such
condition we can represent the molecule as a simple four-state
system ignoring the higher state altogether. For doing so for
convince we are using an operator, known as spin Hamiltonian,

35
Its eigenvalues are same as those of original Hamiltonian within
fourfold state and eigenfunctions give the spin of the state.
Each electron spin operator in two electron system must satisfy
Si2 = 12 (1 + 12 ) = 34 . So total spin must satisfies
3
Si = (S1 + S2 )2 = + 2(S1 .S2 ) (4.17)
2
Since eigenvalue of of S 2 is S(S+1), it follows from above equa-
tion S1 .S2 operator has the eigenvalue -3/4 in singlet and +1/4
in the triplet states. So the operator

1
H = (Es + 3Et ) − (Es − Et )(S1 .S2 ) (4.18)
4
Has eigenvalueEs in singlet state and Et in triplet state.
If we redefine zero of the energy the spin Hamiltonian becomes

Hspin = (−JS1 .S2 ), J = Es − Et (4.19)

As Hspin is scalar product of two operator S1 andS2 it will

favor parallel spin if J is positive and anitparallel if J is nega-
tive. In contrast to (4.1) spin Hamiltonian depend on relative
orientation of spin not their direction with respect to R1 − R2 .
When N (large, not N=2)ions of spin S are widely separated
the ground state will be (2S + 1)N - fold degenerate. The spin
Hamiltonian of this degenerate ground State the splitting are
small in compared to other excitation energy. For many cases
spin Hamiltonian is
X
Hspin = − Jij Si .Sj . (4.20)

Where Si is a operator function which eigenvalue gives the

split level. We must note that

36
 1. For only products pair of spin operators to appear in (4.20)
it is necessary that all magnetic ions are far enough.

2. When angular momentum contains both spin and orbital

part, coupling in spin Hamiltonian may depend on absolute
or relative spin orientation.

The spin Hamiltonian (4.20) is known as Heisenberg Hamilto-

nian and Jij is known as exchange coupling constants.

4.5 Direct Exchange ,Super Exchange,Indirect

Exchange,Itinerant Exchange
In direct exchange Magnetic interaction arises from direct coulomb
interaction among electrons from two ions. Indirect

If magnetic ions are separated by nonmagnetic ions. It is

possible for magnetic ions to have a magnetic interaction medi-
ated by electrons in their common nonmagnetic neighbor, this
is known as superexchange.

When magnetic interaction occur between electrons in par-

tially filled f-shells. In addition to their direct exchange cou-
pling, f-electrons are coupled through their interaction with
conduction electrons. This is known as indirect exchange.

Magnetic interaction among the conduction electron them-

selves is called itinerant exchange.

37
4.6 Magnetic interaction in free electron gas
If every one-electron level with wave vector less than kF is occu-
pied by two electron of opposite spin, then ground state energy
is
3 2 3 e2
E = N [ (kf a0 ) − (kf a0 )]Ry (1Ry = ) (4.21)
5 2π 2a0
The first term in (4.21) is kinetic energy and the second term is
exchange energy.
General possibility that leads to net spin imbalance is to fill one
electron level with k less than some k↑ with spin-up electrons,
and each with k < k↓ ,with spin-down electron.
Since (4.21) is exchange interaction only between electrons of
same spin for each electron population
3 3
E↑ = N↑ [ (k↑ a0 )2 − (k↑ a0 )]Ry
5 2π
3 3
E↓ = N↓ [ (k↓ a0 )2 − (k↓ a0 )]Ry (4.22)
5 2π

38
Where total energy and total number of electrons are
N N↑ N↓ k↑3 k↓3 kF
E = E↑ + E↓ = + = 2+ 2= 2 (4.23)
V V V 6π 6π 3π
E takes the (4.21) form ifN↑ = N↓ = N2 .If one can get a lower
energy by dropping the assumption, then ground state will have
a non-vanishing magnetization density
N↑ − N↓
M = −gµB (4.24)
V
and electron gas will be ferromagnetic.
1
Taking N↓ = N and N↑ = 0, E will be E↓ and k↓ will be 2 3 kF
and therefore
3 1 3 1
E = N [ 2 3 (kF a0 )2 − 2 3 (kF a0 )] (4.25)
5 2π
Comparing this with non magnetic case we get, positive kinetic
2
energy is larger by 2 3 and magnitude of the negative exchange
1
energy is larger by 2 3 . Hence energy of fully magnetized state
is lower than that of the unmagnetized state when exchange
energy dominates kinetic energy. This will happen for low den-
sity. As density decrease transition from non magnetic to fully
magnetic ground state occurs when energies (4.21) and (4.25)
become equal.

Criteria for low-density ferromagnetism is invalidated by:

1. Within Hartree-Fock approximation some choose of one-
electron level leads to lower energy then magnetize and non-
magnetic solution.These solution give an antiferromagnetic
ground state at lower density.
2. If spatial range is reduced by letting the electrons screen
exchange interaction, Hartree-Fock approximation is im-
proved.

39
 3. 3. At very low density the free electron gas can be shown
to crystallize, whose description is outside the reach of in-
dependent electron approximation

4.7 Hubbard Model

J. Hubbard proposed a model which contains minimum of fea-
ture necessary to yield both band-like and localized behavior.
In this model vast set of bound and continuum electron level of
each ion is reduced to a single localized orbital level. States of
the model are given by specify in the possible configuration of
each ion. Them Hamiltonian contains two term
a ) a term diagonal in these state, that is just a positive energy
U times the number of doubly occupied ionic level
b ) a term off-diagonal in these state that has a non-vanishing
matrix element between pairs of states that differ by only
single electron moved from one to other ion.
The first term in the absence of second would favor local mag-
netic moments. The second in the absence of first leads to con-
ventional band spectrum and one-electron Bloch levels in which
each electron is distributed through entire crystal. When both
are present analysis is too difficult.

4.8 Localized Moment in Alloy

An ion in isolation having magnetic electronic she’ll may retain
a part of it’s magnetic moment, or none at all ,when placed in
metallic environment.

When small amounts of transition metal elements are dis-

solved in a nonmagnetic metal, resulting alloy may or may not

40
display localized moment. This theory determine the modifica-
tion of consideration taken in Hund’s rule, when ion is embedded
in metal.

If we will ignore all interactions in these conditions there are

still mechanism by which moment can be altered. Depending
upon the position of the level of the ion relative to the metallic
Fermi level, electron might leave ion for the conduction band of
host, or drop from the conduction band into lower-lying ionic
level, thereby altering the moment. As levels of the ion are
degenerate with the continuum of conduction band levels in the
host, there will be a mixing of levels, in which the ionic ones
become spatially less localized, while nearby conduction band
levels have their charge distributions altered. This will alter
intra-ionic energies that will alter net spin.

4.9 The Kondo theory of resistance minimum

The magnetic impurities in dilute alloys act as scattering Cen-
ters, and if they are the predominant type of impurity or lattice
imperfection, then at low enough temperatures the scattering
they cause will be the primary source of electrical resistance.
Nonmagnetic scatters lead to a temperature independent term
toward which the resistivity monotonically drops with decreas-
ing temperature. In magnetic alloys, however, instead of drop-
ping monotonically the resistivity has a rather shallow minimum
occurring at a low (O (10 K)) temperature that depends weakly
impurities.

This minimum was shown by J. Kondo to arise from some un-

expected features of the scattering of conduction electrons that
arise only when the scattering center has a magnetic moment.
This exchange leads to scattering events in which the electronic

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spin is flipped. This scattering was treated only to leading order
in perturbation theory and was found not to differ qualitatively
from nonmagnetic scattering. Kondo However in all higher or-
ders of perturbation theory the magnetic scattering cross section
is divergent, yielding an infinite resistivity.

The divergence depends critically on there being a sharp

cutoff in the conduction electron wave vector distribution, as
there is at T=0.Further analysis shows that the thermal round-
ing of the electron distribution removes the divergence, yielding
in term in the impurity contribution to the resistivity that in-
crease with decreasing temperature. It is the balancing of this
term against the photon contribution that result in resistance
minimum.

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