Magnetic interactions

Direct exchange in solids:

present but small because d and f orbitals are localized
normally short ranged, and cannot explain the long range ordered magnetic
structure

Superexchange
Magnetic ions interact by charge overlap with same non-magnetic ions
short range, F or AF

Double exchange
encountered in mixed valence compounds
F

Indirect exchange
Magnetic ions interaction mediated by interaction with conduction elections
RKKY (long range, oscillating sign)

Itinerant exchange

The Exchange Interaction

Central for understanding magnetic interactions in solids
Arises from Coulomb electrostatic interaction and the Pauli exclusion
principle

Coulomb repulsion
energy high

UC =

e2
4 0 r 2

Coulomb repulsion
energy lowered

~ 10 18 J (105 K !)

Consider two electrons in an atom:

Hamiltonian:

H = H 1 + H 2 + H 12
H1 =

Ze
1
2me
4 0 r1

r12

er1

2
Ze 2
2
H2 =
2me
4 0 r2
H 12 =

e2
4 0 r12

+
Ze
2
2
2
j = 2 + 2 + 2
x j y j z j

Using one electron approximation:

1
[(1 r1 )2( r2 ) + 2( r1 )(1 r2 )]
2
1
[(1 r1 )2( r2 ) 2( r1 )(1 r2 )]
A( r1, r2 ) =
2

(s r1, r2 ) =

1,2

e- 2
r2

singlet
triplet

are normalized spatial one-electron wavefunctions

We can write energy as:

E=

H
E=

1
*
*
*
*
3
3
[
]
H
H
H

(
r
)
(
r
)
(
r
)
(
r
)
(
)
(
r
)
(
r
)
(
r
)
(
r
)
d
r
d
r2 =

+
+

1
2
3
1 1 2 2
2 1 1 2
1 1 2 2
2 1 1 2
1

= 1(* r1 )H 1(1 r1 )d 3 r1 + 2(* r1 )H 12( r1 )d 3 r1 + 1(* r2 )H 2(1 r2 )d 3 r2 + 2(* r2 )H 22( r2 )d 3 r2

+ 1(* r1 )2(* r2 )H 12(1 r1 )2( r2 )d 3 r1d 3 r2 + 2(* r1 )1(* r2 )H 122( r1 )(1 r2 )d 3 r1d 3 r2
1(* r1 )2(* r2 )H 122( r1 )(1 r2 )d 3 r1d 3 r2 2(* r1 )1(* r2 )H 12(1 r1 )2( r2 )d 3 r1d 3 r2
Individual energies (ionization) = 2I1 + 2I2

Coulomb repulsion = 2K12

Exchange terms =2 J12

E = I1 + I 2 + K12 J 12
Lowest energy state is for triplet, with E = I1 + I 2 + K12 J 12
Parallel alignment of spins lowers energy by:

J 12

e2
1
*
*
3
3

=
(
r
)
(
r
)
(
r
)
(
r
)
d
r
d
r2

1
1
2
2
2
1
1
2
1

4 0
r1 r2

(if J12 is positive)

We can add spin wavefunctions explicitly into previous definitions:

(s r1, r2 ) =

1
[(1 r1 )2( r2 ) + 2( r1 )(1 r2 )][( 1) ( 2 ) ( 2 ) ( 1)]
2

(singlet)

( 1)( 2 )

1
[(1 r1 )2( r2 ) 2( r1 )(1 r2 )] ( 1) ( 2 ) + ( 2 ) ( 1) (triplet)
A( r1, r2 ) =
2

( 1) ( 2 )

1 Spin +1/2
+
+ + =
0
0

= Spin -1/2
1
Heisenberg and Dirac showed that the 4 spin states above are eigenstates
of operator S1 S 2
Hamiltonian of interaction can be written as (called exchange energy):

H ex = 2 JSi S j

J is the exchange parameter (integral)

Superexchange
magnetic atoms are separated by non-magnetic ions (oxygen)
Indirect interactions through Oxygen

Superexchange: due to hybridization

pz wave function is mixed with dz2 orbitals

If A and B are antiparallel, pz hybridize with A and pz hybridize with B

If A and B are parallel: pz hybridize with A and B, but no hybridization for pz

Energy difference of the 2 configurations:

b4
E = E E
d p

hybridization

Orbital vs. Magnetic Ordering

Orbital ordering influence the superexchange interactions because the
lowering of local crystal field symmetries affect the spatial part of
wavefunctions, and thus the hopping integrals
The orbital configurations and the resulting ferromagnetic or
antiferromagnetic exchange interactions are summarized in the:
Goodenough-Kanamori rules
Exchange interaction of two half-filled orbitals is strong and
antiferromagnetic (AFM)
Exchange interaction of half-filled and empty (or doubly-filled) orbitals is
weak and ferromagnetic (FM )

Sign and value of superexchange depends on the M - O M angle and on

the d orbitals involved in the bond, hence it can be of different strengths
and signs in the different directions of the crystal.

Antiferromagnetic Superexchange interactions

t pd= effective hopping

Strong AF coupling:
Weak AF:

Ex.: Most of transition-metal oxides, , LaMnO3, KCuF3

Ferromagnetic Superexchange interactions

Ex.: Spin ladders, zig-zag spin chains,

exotic magnetic structures

Weak F:

Overlap between an occupied

and an unoccupied orbital

Ex. : Low dimensional magnetic

systems (1D or 2D magnetic
structures)

Weak F:

Double exchange
Double exchange leads to ferromagnetism/ferrimagnetism: the transfer of the
minority spin can occur only if majority spins are aligned parallel

Indirect Exchange
Rare Earths
Band overlap is small in f electron atoms weak exchange
field.
At low temperatures, exchange occurs between the f
electrons and nearly free electrons that gives rise to FM in
these materials.
Indirect exchange occurs:
If f electrons around one atom are spin down, then an exchange
interaction will lower the energies of nearby spin up free electrons.
These free electrons then move to other atoms, where exchange
tends to lower the energy of spin down f electrons.

RKKY Interaction
Indirect exchange interaction between RE ions mediated by the
conduction electrons
It is called also RKKY (Ruderman, Kittel, Kasuya and Yoshida) interaction
Let us consider a localized spin S located at r =0 interacting with the spin of the
conduction electron si located at r =ri

H int

= J S si (ri )
i

Each electron feels:

H int

J
H eff =
S (r )
g B

= g B H eff si
i

This field induces the electron spin density at the point r that can be expressed
through the spin susceptibility.

J
3
M (r ) = d r (r r )H eff =
(r )S
g B


Since: M (r ) g B s (r )


J
s (r ) =
(r )S
2
(g B )

 The electron spin acts on the spin S located at r . As a result:

J2
H RKKY =
(r )S S
2
( g B )

iqr sin 2k F r 2k F r cos 2k F r

1
(r ) = (q )e
q
(2k F r )4

JRKKY

cos 2k F r

r3

The coupling is oscillatory and can be

ferromagnetic or antiferromagnetic,
depending on the separation of
neighboring atoms.