Outline

Para-, ferro-, antiferro-, ferrimagnets, ...

Classical theory

Langevine theory of paramagnetism, Curie law

Weiss molecular field theory, T
C
, Curie-Weiss law

Quantum theory of dia- and paramagnetism

Larmor, van lec!, "rillouin function, Pauli

#nteraction of moments
$eitler-London model of $
%
and e&change interaction

$eisen'erg model hamiltonian

mean field appro&imation, Curie-Weiss law, T
C

(uantum $eisne'erg model, magnons, "loch)s law

*toner model

Types of magnetic structures

Classical theory of paramagnetism

+odel of Langevin , magnetic moment as a vector in magnetic field

-nergy of moment m in field H./0,0,$12

+ean value of magneti3ation on atom

where Langevin function is defined as

*uscepti'ility /for large T1

Curie law /inverse proportionality to T1

Weiss molecular field theory

4ttempt to e&plain magnetic order

#ntroduction of an internal field caused 'y neigh'oring atomic moments

$uge fields 56000T7 8o physical interpretation 'y Weiss

#n 3ero e&ternal magnetic field, using Langevin theory

we get 9 graphical solution2

:or T;Tc there is only a solution +.0

Critical temperature

*uscepti'ility 9 Curie-Weiss law

Towards (uantum theory

Langevin)s and especially Weiss theories descri'e a wide range of magnetic

phenomena relatively well

paramagnetism, ferromagnetism, antiferromagnetism /8<el , 8o'el pri3e 6=>01,

ferrimagnetism , 'oth latter cases can 'e (ualitatively descri'ed as two non-
e(uivalent su'lattices generating the internal magnetic field on each other

lac! of mechanism for the internal magnetic field

the Langevin)s function does not fit too well for many systems

no e&planation of magnetocrystalline anisotropy, metamagnetic transitions, etc.

Quantum theory

improves over the Langevin)s function and provides e&planation of the internal
magnetic field

insight into +4-, crystal field e&citations, ...

complete a' initio theory of magnetism consistently treating locali3ed and 'and
character of electrons is still lac!ing

+acroscopic definitions

Thermodynamics2 free energy

+agneti3ation

*uscepti'ility

:orce in inhomogeneous magnetic field

-lectrons in magnetic field

change of canonical momentum operator

the !inetic energy operator 'ecomes

add interaction of spins with magnetic field

summary of new terms in $amiltonian

Pertur'ation theory

the new terms are small at fields which we can produce in la'oratories,
therefore we treat it as a pertur'ation

suscepti'ility is %
nd
order in H

changes in energy levels up to %

nd
order in H2

the linear term is of the order of 56 me in fields 560 T, the other terms are
?-@ orders of magnitude smaller

individual terms lead to a dia- or paramagnetic 'ehavior of the system in

magnetic field

Larmor diamagnetism

insulators, closed shells in ground state /L.S.J.01, i.e., only last term
contri'utes

ground-state energy change due to mag. :ield2

if all e&cited states are high in energy, then

This is Larmor diamagnetic susceptibility /negative1, typically 560

-A

$und)s rules
/61 +a&imi3e the total spin S.
4.!.a. Bthe 'us seat ruleC.
+a&imi3ing spin reduces screening and
allows electrons to get closer to cores.
/%1 While fulfilling /61, ma&imi3e the
total or'ital momentum L.
Classically2 or'iting in the same direction reduces pro'a'ility
that electrons meet, i.e., reduces repulsion.
/?1 :or less than half-filled shells D . EL-*E and for more
than half-filled shells D . L F *.
This is a conse(uence of spin-or'it coupling

an-lec! paramagnetism

if D.0, 'ut not L or *, the first term vanishes

we get two non-3ero terms in suscepti'ility

first term is Larmor diamagnetism

second term is an-lec! paramagnetism /positive1

if the first e&cited state is close in energy to the ground state, more
complicated formulas apply

Paramagnetism

:or atoms with unfilled shells with non3ero *, L and D, the first term is non3ero
and dominates

We have /%DF61 degenerate state in 3ero field

#n non3ero field we need to diagonali3e /%DF61&/%DF61 matri& with elements

Wigner--c!art theorem states

with Land< factor

Paramagnetism

Than!s to Wigner--c!art theorem we see that the matri& is actually diagonal

we can interpret /within the lowest D-multiplet1
as a magnetic moment of the ion

To get suscepti'ility we need to consider all these /%DF61 states split 'y
magnetic field

:ree energy

"rillouin function
:rom free energy we get magneti3ation
where "rillouin function is defined 'y
4t low temperatures B
J
.6
4t high temperatures

Curie)s law

4t high temperatures we get for suscepti'ility

i.e., suscepti'ility is inverse-proportional to temperature , Curie law

This paramagnetic suscepti'ility is at room temperature of the order of 60

-%
-
60
-?
and thus dominates the diamagnetic contri'ution

Comparing to the Curie-law derived in the classical case, we can define an

effective moment G effective "ohr magneton num'er p2

-&ample2 rare-earth paramagnets
Hood agreement theory-
e&periment,
e&cept for *m I -u
*m I -u have low-lying e&cited
states, which we neglected

-&ample2 ?d transition metals
:or ?d transition metals Curie)s
law wor!s if we assume L.0
Quenching of or'ital momentum
due to crystal field splitting
+odification of the third $und)s
rule

+agnetism of conduction electrons

Jelocali3ed conduction electrons

+agnetic field shifts energy levels 'y

*ince we can e&pand density of states

and o'tain for num'er of occupied states
i.e., the magneti3ation is

Pauli paramagnetism

:rom magneti3ation
we get a suscepti'ility
which is independent of temperature

This contri'ution is called Pauli paramagnetism

#t is of order 60
-K
, i.e., compara'le to Larmor diamagnetic contri'ution

8ote2 conduction electrons also have Landau diamagnetic contri'ution to

susc., see 4I+

*ources /%%.@. I %A.@.1

+ain source2
4shcroft I +ermin2 Solid State Physics

Chapter ?62 Jiamagnetism and Paramagnetism /%%.@.1

Chapter ?%2 -lectron #nteractions and +agnetic *tructure

Chapter ??2 +agnetic Ordering

*ee also2
+ohn2 Magnetism in the Solid State

Chapter >2 $eisen'erg $amiltonian

*ection 6K.62 $eitler-London Theory for the -&change :ield

#nteraction 'etween moments

We developed a (uantum theory of magnetic suscepti'ility originating from

various terms /Larmor, van lec!, non3ero-D paramagnetism, Pauli1

*o far we included no interaction 'etween moments 9 no mechanism for a

spontaneous magneti3ation in 3ero e&ternal magnetic field

Possi'le sources of such interaction2

Jipolar , too wea!, 50.6me

*pin-or'ital , stronger in heavy elements, up to 56e for actinides

-lectro-static F Pauli principle , the strongest, 56e and more

$eitler-London model of hydrogen molecule as a starting point for

constructing model $amiltonians for interactions of locali3ed moments

$ydrogen molecule /summary1

Two electron system, four possi'le spin arrangements

We can classify them as

spin singlet /*.01 and
spin triplet /*.612

The ground state is singlet

#f we neglect all the higher e&cited states and restrict ourselves to singlet I
triplet, we can reproduce the energy levels 'y the following model
$amiltonian e&pressed in spin-space only2

$eitler-London model of $
%

% hydrogen atoms, % electrons, assumption that there is always one electron

close to every proton 9 symmetric and antisymmetric wavefunctions

the complete $amiltonian can 'e written as

energies of the spatially symm.Gantisymm. states are

where

$eitler-London model of $
%

Let)s add spins 9 possi'le spin configurations for two electrons2

*.0, +
*
.0 , spin singlet , antisymmetric in spins
*.6, +
*
.-6,0,6 , spin triplet , symmetric

Total %-electron wave-function is always antisymmetric 9 lower lying state

that is symmetric in or'ital space must have antisymmetric spin part, i.e.,
spin singlet I higher lying state, which is antisymmetric in or'ital space will
have 'e a spin triplet

Lsing relations
the same energy levels can 'e directly o'tained 'y

we introduced Be&change constantC 9 generali3ation gives $eisen'erg

model hamiltonian

$eisen'erg model

Henerali3ation of the situation with hydrogen molecule2

-&tracting J
ij
is not a trivial pro'lem and to some e&tent it is still not
completely solved

*olving the (uantum model itself without appro&imations is computationally

unsolva'le e&cept for smallest systems
+echanismsGsources of J
ij
/Olle)s lecture ne&t wee!12

Jirect e&change

*uper-e&change

#ndirect e&change /MNNO1

#tinerant e&change

+agnetic structures

D;0 for nearest neigh'ors 9 ferromagnet

DP0 for nearest neigh'ors 9 antiferromagnet

non-negligi'le D)s for more distant neigh'ors or in geometries leading to

magnetic frustrations 9 more complicated magnetic structures, e.g., spin
spirals, non-collinear structures, etc.

+ean-field theory , Weiss field

rewrite the $eisen'erg model, including field2

this loo!s li!e a set of spins in effective field

which does not depend on i due to periodicity

yet, the effective /Weiss1 field is an operator 9 the mean-field theory

replaces it with its thermodynamic mean value

Critical temperature

Ta!ing mean-field appro&imation and 3ero e&ternal field we o'tain e(uation

When M/T1 goes to 3ero, and we get

the mean-field appro&imation of the magnetic transition temperature
Wea! points2 over-estimation of T
C
, wrong low-temperature 'ehavior, also
around T
C

+ore advanced methods

Mandom-phase appro&imation

+onte-Carlo simulations , e&act answers within the classical $eisen'erg

model, though demanding calculations

Lsing numerical methods we can also get M/T1 within all three methods

Joing +onte-Carlo $eisen'erg model (uantum-mechanically is still an

active field of research

Hround state of ferromagnet

4t T.0, all moments aligned parallel, i.e., total moment 8* 9 E8*,8*;

Mewrite $eisen'erg $amiltonian using raising and lowering operators2

4pplying the $$ on the E8*,8*; gives

i.e., it is an eigenstate of the $$

8o lower energy-state of ferromagnetic $$ e&ists 9 it is a ground state E0;

$int2

Low-T e&citations of ferromagnet

Lowering spin proQection 'y one at one site is not an eigenstate of $$2

"ecause , i.e., translational invariance, we

can construct linear com'inations
which are eigenstates of $eisen'erg $amiltonian2

One can show that

Low temperature magneti3ation

*uperposition of magnons /li!e for phonons1 is only an appro&imation here,

'ut B(uite ONC for low-lying e&cited states

The magneti3ation is reduced 'y one per magnon, i.e.

4t low temperatures only the lowest

energy e&citations happen, and for these
i.e.,
"loch)s ?G% law

+ermin-Wagner theorem 9 no magneti3ation in %J or 6J

Hround state of antiferromagnet

#ntuitively2 arrangement of alternating upGdown moments

#t is not an eigenstate of $eisen'erg $amiltonian7

4ssume *.6G% chain and apply

#n classical case /spins as vectors1 this is a ground state with lowest energy

:or nearest-neigh'or /881 interaction the following 'ounds are valid2

which actually coincide in the classical case, where
Q i Q i