MagneticPropertiesofSolids

JS3015 J.M.D.Coey

10lectures+Tutorial

Recommendedbooks

StephenElliot:ThePhysicsandChemistryofSolids,Wiley1998:Ch7

Therecommendedsolidstatetext.Ch7treatsdielectricsfirst.Thereisacloseanalogybetweendielectric
andmagneticmaterials,andbetweenferroelectricityandferromagnetism.

StephenBlundellMagnetisminCondensedMatter,Oxford2001
Anewbookprovidingagoodtreatmentofthebasics

J.Crangle;TheMagneticPropertiesofSolids,Arnold1977:1990
Ashortbookwhichtreatsthematerialatanappropriatelevel.

DavidJilesIntroductiontoMagnetismandMagneticMaterials,Chapmanand
Hall1991;1997
Amoredetailedintroduction,writteninaquestionandanswerformat.

Mondayat1700,Wednesdayat1100,1200
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1Introduction
2Basicconcepts
3.Magnetismoftheelectron
4.Magnetismoflocalizedelectronsontheatom
5Paramagnetism
6.Ferromagnetism.
7.MiscellaneousTopics
8.MagneticApplications

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1Introduction
1.1
Historicalbackground.See
'MagnetismThroughtheAges'onthewebpage.
1.2
Magnetizationandhysteresis;
Overview

5Paramagnetism
5.1
ClassicalTheory
5.2
Quantumtheory
5.3
Paramagnetismofmetals

2Basicconcepts
2.1Momentsandfields
2.2Magneticfieldcalculations
2.3
Units
2.4Dimensions

6.Ferromagnetism.
6.1
Meanfieldtheory
6.2
ExchangeInteractions.
6.3
Ferromagneticdomains
6.4
Magneticmeasurements

3.Magnetismoftheelectron
3.1
Orbitalmoment
3.2
Spinmoment
3.3Magnetismofelectronsinsolids.
3.4Localizedanddelocalizedelectrons
3.5Theoryoftheelectronicmagnetism

7.MiscellaneousTopics
7.1
Antiferromagnetism
7.2
Ferrimagnets.
7.3
Otherformsofmagneticorder
7.4
Spinwaves
7.5
Magneticneutronscattering

4.Magnetismoflocalizedelectronsontheatom
4.1
Thehydrogenicatomandangular
momentum.
4.2Themanyelectronatom.
4.3Spinorbitcoupling
4.4
Zeemaninteraction
4.4Ionsinsolids

8.MagneticApplications
8.1
Hardmagnets
8.2
Softmagnets
8.3
Magneticrecording
8.4
Spinelectronics

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1 Introduction

1.1Historicalbackground.See'MagnetismThroughtheAges'onthewebpage.
1.2 Magnetizationandhysteresis;Courseoverview.

A wonder I experienced as a child of 4 or 5 years, when my father showed me a compass. That this
needle behaved in such a determined way did not at all fit into the nature of events. I can still
remember or at least I believe I can remember that this experience made a deep and lasting
impression on me.
Albert Einstein

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Table1.Thesevenagesofmagnetism
GE

Time

KeyNames

Driver

Achievements

Materials

1000
to
1500

ShenKua
Petrus
Peregrinus

State

ncient

Forcefield,
Induced
magnetism,
Thermoremanenc
e

Iron,
Lodestone

Applications/
Devices
Southpointer,
Compass

1500
to
1820

Gilbert
Descartes
D.
Bernoulli

Navy

Earthsfield

arly

Iron,
Lodestone

Dipcircle.
Horseshoemagnet

1820
to
1900

Oersted,
Ampere,
Faraday,
Maxwell
Hertz

Industry
(infrastruc
ture)

Electromagnetic
induction,
Maxwells
equations

Electricalsteels

ectromagne
Elecro-

1900
to
1935

Weiss,
Bohr,
Heisenberg,
Pauli,
Dirac,
Landau

Academy

Spin,
Exchange
interactions

(Alnico)

Bloch,
Pound,
Purcell

Military

Microwaves,
EPR,FMR,
NMR

Ferrites

Radar,
Television

Industry
(consumers)

New
Materials
miniaturisation of
magneticcircuits

NdFeB,
SmCo

Consumerelectronics

Industry
(consumers)

Thinfilmdevices

Multilayers

High density magnetic

recording,MRAM

Age
Ancient

Early
scientific

magnetic

nderstandin

Underrstanding

1935
gh High
to
equency
frequency 1960

pplications

Applications

1960
to
1995

1995
pin Spin

ectronics
electronics

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Motors, Generators,
Telegraph,
Wireless,
Magneticrecording

The Ancient Age

-1000 to 1500
Key names

Applications

Shen Kun

South-Pointer

Petrus Peregrinus

Compass

Scientific achievements
Force field
Induced magnetism

Driver

Thermoremanence

The State

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The Electromagnetic Age

1500 - 1800
Applications

Key names

Motors, Generators

Oersted, Ampere

Telegraph, Wireless

Faraday, Maxwell

Magnetic recording

Hertz

Scientific Achievements

Driver

Electromagnetic Induction

Industry
(Infrastructure)

Maxwells Equations
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The Age of Understanding

1900 - 1935
Applications

Key Players
Weiss, Bohr
Heisenberg

H = 2JSiSj

Dirac, Pauli
Landau

Scientific Achievements
Spin, Mean Field Theory

Driver

Exchange Interactions

Academy

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The Age of Applications

1960 - 1995
Key Players

??

Applications

Consumer
Electronics

Scientific Achievements

New materials
Miniaturisation of Magnetic Circuits
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Driver

Industry
(Consumer)
11

Magnetapplications;A30Bmarket

Others
Amorphous

Soft ferrite

Hard ferrite

Ni-Fe/Fe-Co

Hard
Magnets
Nd-Fe-B
Sm-Co

Fe-Si (oriented)

Alnico
Others

Soft
Magnets

Co- Fe 2 O 3
(tapes, floppy discs)
CrO2 (tapes)
Iron (tapes)

Fe-Si
Co-Cr (hard discs)

Magnetic
Recording

Iron
Others

Ni-Fe/Fe-Co (heads)

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The Age of Spin Electronics

1995 - ?
Albert Fert
Peter Gruneberg
Stuart Parkin

Applications

High-density
recording
MRAM

Scientific Achievements

Thin film devices

Driver

Industry
(Consumer)
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13

Magnetization and hysteresis

The irreversible, nonlinear response of a ferromagnet to an applied magnetic field is described by the
hysteresis loop, which reflects the arrangement of the magnetization in ferromagnetic domains. The loop
is nonlinear and multivalued (history dependent). Note that the magnet cannot be in thermodynamic
equilibrium anywhere around the open part of the curve! Important parameters are the remanent
magnetization Mr` and the coercive field Hc.

Advances in magnetic materials and magnet applications have been due essentially to mastery of
coercivity. We have a wide range of soft (narrow loop), hard (broad loop) and intermediate magnetic
materials. The hard materials are used for permanent magnets. The soft materials are used in
electromagnetic machines (motors, generators, transformers). The intermediate materials are used for
magnetic recording media
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2 Basic Concepts
ThissectionintroducesthemagnetizationMandthetwomagneticfieldsBandH.Thesearevectorswhichare
definedateverypositionrinasolid.Unitsanddimensionsinmagnetismarediscussed .

2.1
Momentsandfields
Magnetization
Magnetizationisthebasicmagneticquantityinasolid.Itoriginatesfromtheatomicelectrons,
whicharethecarriersofmagneticmoment.
m
I

Allmagnetismisduetocirculatingcurrents,Therelationforacurrentloopis
m=IA
misthemagneticdipolemoment,Iistheelectriccurrent,Aistheareavector.UnitsofmareAm2.
Itisapolarvector.Directionisgivenbythecorkscrewrule.
ThemagnetizationMofasolidisthemagneticdipolemomentperunitvolume.

M=m/V
UnitsofMareAm1.Formanypurposes,theatomicscalestructurecanbeneglected.Mis
regardedasasmoothlyvaryingvector(Vcontainsmanyatoms).
Themagnetizationofiron,forexample,is1.76MAm1(Imaginethecurrents)
Estimatethemagneticmomentofaferritefridgemagnet(M0.2MAm1)
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Bfield
ThemagneticfieldBproducedbythecurrentloopisdivergenceless(solenoidal).Therearenomagnetic
monopolesinNaturetoactassourcesorsinksofB.(ComparewithE)
B

B=0MaxwellsEquation
Thevectoroperatormeans(/x,/y,/z).
''isthedivergence(div)ofavector.Thescalar
productBx/x+By/y+Bz/z

UnitsofBareTesla.(abbreviationT)
TheBfieldisalsoknownasthemagneticfluxdensity.Fluxisdefinedas=SB.dA,orforauniform
fieldnormaltoanareaA,=BA.
B=0canbewritteninanequivalentintegralformoveranyclosedsurfacesasSB.dA=0
Inotherwordsthefluxthroughanyclosedsurfaceiszero,.=0.
ThereisalittleusedSIunitforflux,theWeber.1T=1wbm2
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TherelationbetweentheBfieldandcurrentdensityj(unitsAm2)inthesteadystateisgivenby
anotherofMaxwell'sequationswhichcanalsobewritteninpointformorinintegralform.Weassume
notimevariation.i.e.magnetostatics.
Inpointform,
oj
Here0isthemagneticconstant0=4107TmA1.
''istherotation(curl)ofavector
isgivenbytheexpressionex(By/zBz/y)+ey(Bz/xBx/z)+ez(Bx/yBy/x)
Inintegralform,aroundanyclosedloopthreadedbyanetcurrentI

Slide 10

loopB.dl=0I
loop

ThisequationisknownasAmpere'slaw.

Animportantresult:Itispossibletocalculatethefieldduetoasmallcurrentloopm=IA.Theresult
withcomponentsinpolarcoordinatesis
Bdip=(0m/4r3)[2coser+sine]
Thisisequivalenttothefieldduetoanelectricdipole(itfallsoffasr3,andisanisotropicbeingtwice
asgreatintheaxialpositionasinthebroadsideposition).Hencethemagneticmomentmiscommonly
knownasthemagneticdipolemoment.
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Hfield
Thedifficultywhenwearedealingwithmagneticsolidsisthatthecurrentdensityjismadeupof
contributionsfromcurrentsinexternalcircuitsj0(whichwecanmeasure)andcontributionsfromthe
atomiccurrentsjMthatcreatethemagnetizationofasolid(currentswecannotmeasure).
TherelationbetweenjMandMisjM,and 0(j0+jM).Henceitfollowsthat
0M)0j0.DefineH=0M)
or

B=0(H+M)

NowweareabletoretainAmpere'slawforthefieldH,whichdoesnotdependontheunmeasurable
currentsjM.Inpointform,j0orinintegralformloopH.dl=I0
TheHfieldisnotsolenoidal.Itwillhavesources(orsinks)wherever
,e.g.atthe
surfaceofamagnet.(ThesearethefabledNorthandSouthpoles).
NotethattheHfieldisnotcreatedbyconductioncurrentsonly.Anypieceofmagnetisedmaterial
createsanHfieldbothinthespacearoundit,andwithinitsownvolume.Generallythefieldata
pointisH=Hd+H0,whereH0isthefieldcreatedbycurrentsincircuits,andHdisthefieldcreated
bythemagnetitself,whichisknownasthe strayfieldoutsidethemagnet,andthe demagnetizing
fieldinsidethemagnet.
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B,HandM
ThedistinctionbetweentheBfieldandtheHfieldinfreespaceistrivial.Theyareproportional,but
withdifferentunits.ThusB=0H.
SincetheratioB/H,whenthesequantitiesareproportional,isknownaspermeability,0is
thepermeabilityoffreespace.
H

QuickTime and a GIF decompressor are needed to see this picture.

Inside a magnetic material, B and H are completely different, as shown above for a uniformly
magnetizedbarmagnet.TherelationB=0(H+M)atapointPisillustratedbythelittlevectordiagram.
Notethatinsidethemagnet, BandHareoppositelydirected,and Hisoppositeto M.Hencetheterm
demagnetizingfield.HisimportantinsolidsbecausethemagnetizationstateisdeterminedbyH(r)
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Boundaryconditions
Atanyinterface,itfollowsfromSB.dA=0thattheperpendicular
componentofBiscontinuous,andfromAmpereslawloopH.dl=I0
=0(therearenoconductioncurrrentsonthesurface)thattheparallel
componentofHiscontinuous.

H||

Externalfields
InfreespaceanexternalfieldH(orB),whichcouldbecreatedbyconductioncurrentsormagnetsor
Both,interactswithamomentmandmodifiesitsenergy.Theenergyis
E=0m.H(i.e.mBcos)
B

Differentiatinggivesthetorque=E/ TheforceonamagnetF==(m.B).=0mH
m
(i.e.mBsin)
Itdependsonthefieldgradient
(thecompassisanexample)
Thereisnonetforceinauniformfield.
NotethatwheneverHinteractswithmatter,0comesintotheequation,
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Demagnetizingfields
TherelationbetweenH,theinternalfieldinamagnetandtheexternalfieldHextis
H=Hext+Hd
ThereisasimpleexpressionforHdinthecaseofauniformlymagnetizedellipsoid
Hd=NM
AconstraintonthevaluesofNwhenMliesalongoneoftheprincipalaxes,x,y,z.isNx+Ny+Nz=1
Itiscommonpracticetouseademagnetizingfactortoobtainapproximateinternalfieldsinsamples
ofothershapes(bars,cylinders),whichmaynotbeuniformlymagnetized.
N
Examples.
Longneedle,Mparalleltothelongaxis,a
0
Longneedle,Mperpendiculartothelongaxis
1/2
Sphere

1/3

Thinfilm,Mparalleltoplane
Thinfilm,Mperpendiculartoplane

0
1

Toroid,Mperpendiculartor

Generalellipsoidofrevolution

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Nc=(1Na)/2
21

The state of magnetization of a sample depends on H, ie M = M(H). H is the independent variable.

Hext

Ms /3

HH
ext

H'
H

Magnetization curves for a ferromagnetic sphere, showing the variation of magnetization as a function
of the external and internal fields. Themagnetizationofauniformsoftellipsoidadjustsitselfsothat
H=0uptosaturation.
Magnetization, Susceptibility and Permeability
Therelativesusceptibilityrisdefinedinsmallfieldsasr=M/H.Notethatrhasnounits.Most
materialsareparamagnetsordiamagnets.Theirsusceptibilityissmallandpositiveornegative,
repectively.(magnitude104107).Ferromagnetshavelargepositivesusceptibilities(10105).Forthe
specialcaseofauniform,softferromagneticellipsoidshownabove,thesusceptibilityinanexternalfield
is1/N.Arelatedquantityisthepermeability,definedforaparamagnet,orasoftferromagnetinsmall
fieldsas=B/H. SinceB=0(H+M),itfollowsthat=0(1+r).Therelativepermeabilityr=/0
=(1+r)
Inpracticeitismucheasiertomeasurethemassofasamplethanitsvolume.Measuredmagnetisation
is=M/,themagneticmomentperunitmass(isthedensity).Likewisethesusceptibilityisoften
definedas=/B
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2.2Unitsanddimensions
WeuseSIthroughoutwiththeSommerfeldconventionB=0(H+M).Engineerspreferthe
KenellyconventionB=0H+J,wherethepolarizationJis0M.BothareacceptableinSI.
ThepolarizationofironisJ=2.16T.
FluxdensityBandpolarizationJaremeasuredintelsa(alsomT,T).Magneticmomentmismeasured
inAm2sothemagnetizationMandmagneticfieldHaremeasuredinAm1.Fromtheenergyrelation
E=m.B,itisseenthatanequivalentunitformagneticmomentisJT1,somagnetizationcanalsobe
expressedasJT1m3.,themagneticmomentperunitmassinJT1kg1,isthequantitymostusually
measuredinpractice.0isexactly4.107T.mA1.

Theinternationalsystemisbasedonfivefundamentalunitskg,m,s,K,andA.
Derived units include thenewton (N) = kg.m/s2, joule (J) =N.m,coulomb(C)= A.s, volt (V) = JC 1,
tesla(T)=JA1m2=Vsm2,weber(Wb)=V.s=T.m2andhertz(Hz)=s1.
Recognizedmultiplesareinstepsof103,butafewexceptionsareadmittedsuchascm(102m)and
(1010m).Multiplesofthemeterarefm(1015),pm(1012),nm(109),m(106),mm(103)m(100)
andkm(103).
TheSIsystemhastwocompellingadvantagesformagnetism:
(i)itispossibletocheckthedimensionsofanyexpressionbyinspectionand
(ii)theunitsaredirectlyrelatedtothepracticalunitsofelectricity.
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cgsUnits
Muchoftheprimaryliteratureonmagnetismisstillwrittenusingcgsunits.Fundamentalcgsunitsare
cm, g and s. The electromagnetic unit of current is equivalent to 10 A. The electromagnetic unit of
potential is equivalent to 10 nV. The electromagnetic unit of magnetic dipole moment (emu) is
equivalentto1mA.m2.Derivedunitsincludetheerg(107J)sothatanenergydensitysuchasK1of
1Jm3isequivalentto10ergcm3.Theconventionrelatingfluxdensityandmagnetizationis
B=H+4M
wherethefluxdensityorinductionBismeasuredingauss(G)andfieldHinoersted(Oe).Magnetic
moment is usually expresed as emu, and magnetization is therefore in emu/cm3, although 4M is
frequentlyconsideredafluxdensityexpressionandquotedinkilogauss.0isnumericallyequalto
1GOe1,butitisnormallyomittedfromtheequations.ThemostusefulconversionfactorsbetweenSI
andcgsunitsinmagnetismare
B
H
m
M

1TkG
1kAm112.57( 12.5)Oe
1JT11000emu
1kAm11emucm3
1JT1kg11emug1

1G0.1mT
1OeAm1
1emu1mJT1

ThedimensionlesssusceptibilityM/Hisafactor4largerinSIthanincgs.

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Dimensions
IntheSIsystem,thebasicquantitiesaremass(m),length(l),time(t),charge(q)andtemperature().
Any other quantity has dimensions which are a combination of the dimensions of these five basic
quantities, m, l, t, q and . In any relation between a combination of physical properties, all the
dimensionsmustbalance.
Mechanical
Quantity
area
volume
velocity
acceleration
density
energy
momentum
angularmomentum
momentofinertia
force
power
pressure
stress
elasticmodulus
frequency
diffusioncoefficient
viscosity(dynamic)
viscosity(kinematic)
Plancksconstant

Thermal
symbol
A
V
v
a

E
p
L
I
F
p
P
S
K

unit
m2
m3
m.s1
m.s2
kg.m3
J
kg.m.s1
kg.m2.s1
kg.m2
N
W
Pa
N.m2
N.m2
s1
m2.s1
N.s.m2
m2.s1
J.s

m
0
0
0
0
1
1
1
1
1
1
1
1
1
1
0
0
1
0
1

2
3
1
1
3
2
1
2
2
1
2
1
1
1
0
2
1
2
2

0
0
1
2
0
2
1
1
0
2
3
2
2
2
1
1
1
1
1

q
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0

Quantity
enthalpy
entropy
specificheat
heatcapacity
thermalconductivity
Sommerfeld
coefficient
Boltzmannsconstant

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symbol
H
S
C
c

unit
J
J.K1
J.K1.kg1
J.K1
W.m1.K1
J.mol1.K1

J.K1

m l t q
1 2 2 0
1 2 2 0
0 2 2 0
1 2 2 0
1 1 3 0
1 2 2 0
1

2 2

0
1
1
1
1
1

0 1

25

Electrical
Quantity
current
currentdensity
potential
electromotiveforce
capacitance
resistance
resistivity
conductivity
dipolemoment
electricpolarization
electricfield
electricdisplacement
electricflux
permitivity
thermopower
mobility

Magnetic
symbol
I
j
V

C
R

p
P
E
D

unit
A
A.m2
V
V
F

.m
S.m1

C.m
C.m2
V.m1
C.m2
C
F.m1
V.K1
m2V1s1

m
0
0
1
1
1
1
1
1
0
0
1
0
0
1
1
1

0
2
2
2
2
2
3
3
1
2
1
2
0
3
2
0

t
1
1
2
2
2
1
1
1
0
0
2
0
0
2
2
1

q
1 0
1 0
1 0
1 0
2 0
2 0
2 0
2 0
1 0
1 0
1 0
1 0
1 0
2 0
1 1
1 0

Quantity
magneticmoment
magnetisation
specificmoment
magneticfieldstrength
magneticflux
magneticfluxdensity
inductance
susceptibility(M/H)
permeability(B/H)
magneticpolarisation
magnetomotiveforce
magneticcharge
energyproduct
anisotropyenergy
exchangecoefficient
Hallcoefficient

symbol unit
m
A.m2
M
A.m1

A.m2.kg1
H
A.m1

Wb
B
T
L
H

H.m1
J
T
F
A
qm
A.m
(BH)
J.m3
K
J.m3
A
J.m1
RH
m3.C1

m
0
0
1
0
1
1
1
0
1
1
0
0
1
1
1
0

2
1
2
1
2
0
2
0
1
0
0
1
1
1
1
3

t
1
1
1
1
1
1
0
0
0
1
1
1
2
2
2
0

q
1 0
1 0
1 0
1 0
1 0
1 0
2 0
0 0
2 0
1 0
1 0
1 0
0 0
0 0
0 0
1 0

Examples:
1)

Kineticenergyofabody;E=(1/2)mv2
[E]=[1,2,2,0,0]

[m]= [1,0,0,0,0]

2)

Lorentzforceonamovingcharge;F=qvxB
[F]=[1,1,2,0,0]

[q]=

[0,0,0,1,0]

[v]= [0,1,1,0,0]
[B]= [1,0,1,1,0]
[1,1,2,0,0]

[v2]= 2[0,1,1,0,0]
[1,2,2,0,0]

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3)

Domainwallenergyw=AK(wisanenergyperunitarea)
[w]=[EA1]

[AK]=1/2[AK]

=[1,2,2,0,0] [A]=1/2[1,1,2,0,0]
[1,1,2,0,0] []=1/2[1,1,2,0,0]
=[1,0,2,0,0]

[1,0,2,0,0]

4)
Magnetohydrodynamicforceonamovingconductorf=vxBxB(fisaforceper
unitvolume)
[f]=[FV1]

[]= [1,3,1,2,0]

=[1,1,2,0,0]
[0,3,0,0,0]
[1,2,2,0,0]

[v]= [0,1,1,0,0]
[B2]= 2[1,0,1,1,0]
[1,2,2,0,0]

5)
FluxdensityinasolidB= 0(H+M).(Notethatquantitiesaddedorsubtracted
inabracketmusthavethesamedimensions)

6)

[B]=[1,0,1,1,0]

[ 0]= [1,1,0,2,0]

[M],[H]= [0,1,1,1,0]

[1,0,1,1,0]

MaxwellsequationxH=j+dD/dt.
[xH]=[Hr1]
=[0,1,1,1,0]
[0,1,0,0,0]
=[0,2,1,1,0]

[j]=[0,2,1,1,0]

[dD/dt]=[Dt1]

=[0,2,0,1,0]
[0,0,1,0,0]
=[0,2,1,1,0]

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3.Magnetismoftheelectron
Theoriginofmagnetisminsolidsisthequantizedangularmomentumoftheelectrons,withtwodistinctsources;orbitalmotionand
spin. Spin itself and spinorbit coupling are relativistic effects. The description of magnetism in solids is fundamentally different
depending on whether the electrons are localized on the ion cores, or delocalized in energy bands. In this course we focus on
localisedmagnetism

Themagneticpropertiesofsolidsderivefromthemagnetismoftheirelectrons.
The electron is a particle with charge e, mass m, possessing intrinsic angular momentum, known as
spin.
e=1.6021019C

m=9.1091031kg

(Nucleialsopossessmoments,buttheyare 1000timessmaller).

(a)moment
Orbital

(b)
Spin
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3.1Orbitalmoment

The circulating current is I;

The moment is m = IA
-e

Anelectroninacircularorbit,radiusr,isequivalenttoacurrentloop

I = ev/2r
m = evr/2

In Bohrs quantum theory, orbital angular momentum l

isquantizedinunitsof;hisPlancksconstant,6.6226
1034Js;=h/2=1.0551034Js.

Theorbitalangularmomentumisl=rmv;|l|=l;l=1,2,....
listheangularmomentumwithunitsJs,lisaquantumnumber,anintegerwithnounits.Eliminating
rintheexpressionform,
m=l(e/2m)=lB
Theminussignmeansthatmandlareoppositelydirected,sincetheelectronchargeisnegative.
Thequantity(e/2m)isdefinedtobetheBohrmagneton(B),thebasicunitofatomicmagnetism;
B=9.2741024Am2
[Generally,fornoncircularorbits,m=(1/2)vrjMdV;jM(r)=ev(rr);m=erv/2=(e/2m)l
sincel=rmv]
JS3015 - 2003

29

3.2Spinmoment
Theelectronhasamysteriousbuiltinspinangularmomentums.Spinarisesfromrelativisticquantum
mechanics.Thespinquantumnumberis1/2.
|s|=s;s=1/2
Nonetheless,themagneticmomentassociatedwithelectronspinisalso1B.m=2s(e/2m)=1B
Themagnetomechanicalratioisdefinedastheratioofmagneticmomenttoangularmomentum
Fororbitalangularmomentumm=l,hence
=e/2m)
Thegfactorisdefinedastheratioofm(inunitsofB)tol(inunitsof)
g=1fororbitalmotion
Forspinangularmomentum
=e/m)
g=2forspin(afterhigherordercorrections,2.0023)
Spinangularmomentumistwiceaseffectiveasorbitalangularmomentumincreatingamagnetic
moment.
Generallythereisbothspinandorbitalangularmomentumforanatomicelectron.Theyproducea
totalangularmomentumj,j=l+s;j=l1/2.|j|=j.m=g(e/2m)j
Interactionwithmagneticfields
FromE=m.B,wecanseethatifB=1Tandm=1BtheinteractionenergyE(1T)is9.2741024J.
SincekB=1.3811023B/K,E/kB=0.672K/TTheseinteractionsareratherweak,comparedtoRT.
JS3015 - 2003

30

Einsteinde Haas experiment. This demonstrates the reality of the

relationbetweenmagnetizationandangularmomentum.Anickelrod
issuspendedonatorsionfibre.Thefieldinthesolenoidisreversed,
changing the direction of magnetization of the nickel. It rotates, to
conserveangularmomentumastheangularmomentaoftheelectrons
isreversed.
ItturnsoutthatgforNiisg=2.21,sothemomentisessentiallydue
tospin.However,mforNiisonly0.6B/atom.Thereislessthanone
electronwithanunpairedspin,yetthenumberofelectrons/atomZ=
28
3.3Magnetismofelectronsinsolids.

torsion fibre

solenoid

Ni rod

Magnetisminfreeatomsisreducedbyshellfillling.
Electronsinfilledshellshavepairedspinswithnonetmoment.
Onlyunpairedelectronsinunfilled(usuallyoutermost)shellshaveamoment.
Magnetisminsolidstendstobedestroyedbychemicalinteractionsoftheouterelectrons:
electrontransfertoformfilledshellsinioniccompounds
covalentbondformationinsemiconductors
bandformationinmetals

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31

Table3.1Magnetismoffreeatoms

Theonlyelementsthatarenonmagneticasfreeatomsarethoseboxed,inboldtype.
Radioactiveatomsareshowninitalics.Exceptforhydrogen,allmomentsare<<ZB.
JS3015 - 2003

32

Formation of d and sbands in a metal. The

broad sbands have no moment. The dbands
mayhaveoneiftheyaresufficientlynarrow.

QuickTime and a GIF decompressor are needed to see this picture.

Nickelhasaconfiguration3d9.44s0.6.Thereare
0.6unpaired3delectrons,m=0.6B

Existenceofmagnetismdependscriticallyoncrystalstructureandcomposition.
TableAtomicmomentsofironindifferentcompoundsinBohrmagnetons/Fe.
Fe2O3

Fe

YFe2

Fe

ferrimagnet

ferromagnet

ferromagnet

antiferromagnet Pauli
paramagnet

5.0

2.2

1.45

unstable

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YFe2Si2

33

3.4Localizedanddelocalizedelectrons
LOCALIZEDMAGNETISM
Integralnumberof3dor4felectrons
ontheioncore;Integralnumberofunpairedspins;
Discreet energy levels.
with
9
Ni2+
3d8
m=2B
3d

DELOCALIZEDMAGNETISM
Nonintegralnumberofunpairedspins
peratom.
Spinpolarized energy bands
strongcorrelations.
Ni
3d9.44s0.6 m=0.6B

3d

exp(r/a0)
Boltzmannstatistics
4fmetals
4fcompounds
3dcompounds
3dmetals

exp(ik.r)
FermiDiracstatistics

localizedelectrons
localizedelectrons
localized/delocalizedelectrons
delocalizedelectrons.

AbovetheCurietemperature,neitherlocalizednordelocalizedmomentsdisappear,theyjust
becomedisorderedintheparamagneticstate,T>TC.
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34

Susceptibility of localized electrons (Curie susceptibility)

Theelectronshaves=1/2,andg=2.Therearetwostates,alsoknownasspinup(andspindown
(), with ms = 1/2, which correspond to two possible orientations of the moment relative to the
appliedfield.SinceE=m.B,thetwoenergylevelsEi=0gBmsH,aremi=0BH.
ThepopulationofanenergylevelisgivenbyBoltzmannstatistics;itisproportionalto
exp{E(kT}.Thethermodynamicaverage<m>isevaluatedfromtheseBoltzmannpopulations.
z
<m>=[(1/2)gBexp(x)(1/2)gBexp(x)]/[exp(x)+exp(x)]
<m>=mtanh(x)
MmSs
1/2
H
wherex=0BH/kBT.
1/2
S=1/2
Insmallfields,tanh(x)x,hence
g[S(S+1)]B
0BHH
g
B

1/2

r=0N /kBT
2
B

ThisisthefamousCurielawforthesusceptibility,whichvariesasT .
1

1/2

In other terms
r = C/T, where C = 0NB2/kB is a constant with dimensions of temperature;
Assuming an electron density N of 61028 m3 givesC 0.5K.The Curielawsusceptibilityat room
temperatureisoforder1.6103.
Manytwolevelsystemsinphysicsaretreatedbyassigningthemapseudospins=1/2.
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35

Susceptibility of delocalized electrons (Pauli paramagnetism of metals)

The calculation for metals proceeds on a quite different
basis. The electrons are indistinguishable particles which
obey FermiDirac statistics. They are not localized, so
Boltzmannstatisticscannotbeapplied.Theelectronshave
s = 1/2, m = B. They partlyfill some energy band up to
theFermilevelEF.
Aroughcalculationgivesthesusceptibilityasfollows:
r=(N N )B/H

E
EF

H=0

H
0BH

2[N(EF)0gBH]B/HwhereN(EF)isthedensityofstatesattheFermilevelforonespin
direction.
r20N(EF)B2
This is known as the Pauli susceptibility. Unlike the Curie susceptibility, it is very small, and
temperatureindependent,tofirstorder.
The density of states N(EF) in a band is approximately N/2W, where W is the bandwidth (which is
typically a few eV). Comparing the expression for the Pauli susceptibility with that for the Curie
susceptibilityr=0NB2/kBT,weseethatthePaulisusceptibilityisafactork BT/Wsmallerthanthe
Curiesusceptibility.Thefactorisoforder100atroomtemperature.rPauliisoforder105.
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36

[3.6Theoryoftheelectronicmagnetism]
Maxwells equations relate magnetic and electric fields to their sources. The other fundamental
relationofelectrodynamicsistheexpressionfortheforceonamovingparticlewithchargeq,
F=q(E+vB)
ThetwotermsarerespectivelytheCoulombandLorentzforces.Thelattergivesthetorqueequation
= mB The corresponding Hamiltonian for the particle in a vector potential A representing the
magneticfieldB(B=)andascalarpotentialrepresentingtheelectricfieldE(E=e)is
H=(1/2m)(pqA)2+qe
OrbitalMoment
TheHamiltonianofanelectronwithelectrostaticpotentialenergyV(r)=eeis
H=(1/2m)(p+eA)2+V(r)
Now(p+eA)2=p2+e2A2+2eA.psinceAandpcommutewhen.A=0.So
H=[p2/2m+V(r)]+(e/m)A.p+(e2/2m)A2
H=H0+H1+H2
whereH0 istheunperturbedHamiltonian,H1givestheparamagneticresponseoftheorbitalmoment
andH2describesthesmalldiamagneticresponse.ConsiderauniformfieldBalongz.Thenthevector
potentialincomponentformisA=(1/2)(By,Bx,0),
soB=ez(Ay/xAx/y)=ezB.Moregenerally
A = (1/2)Br
Now (e/m)A.p = (e/2m)Br.p = (e/2m)Brp = (e/2m)B.l since l = rp. The second terms in the
HamiltonianisthentheZeemaninteractionfortheorbitalmoment
H1=(B/)B.l

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37

Thethirdtermis(e2/8m)(Br)2=(e2/8m2)B2(x2+y2).Iftheorbitalissphericallysymmetric,<x2>=<y2>=
<r2>/3.ThecorrespondingenergyE=(e2B2/12m)<r2>.SinceM=E/Bandsusceptibility=0NM/B,
Itfollowsthattheorbitaldiamagneticsusceptibilityis=0Ne2<r2>/6m.
SpinMoment
ThetimedependentSchrdingerequation
(2/2m)2+V=i/t
isnotrelativisticallyinvariantbecausetheoperators/tand/xdonotappeartothesamepower.We
needtousea4vectorX=(ct,x,y,z)withderivatives/X.
Dirac discovered the relativistic quantum mechanical theory of the electron, which involves the Pauli
spin operators I, with coupled equations for electrons and positrons. The nonrelativistic limit of the
theory, including the interaction with a magnetic field B represented by a vector potential A can be
writtenas
H=[(1/2m)(p+eA)2+V(r)]p4/8m3c2+(e/m)B.s+(1/2m2c2r)(dV/dr)(1/4m2c2)(dV/dr)/r
Thesecondtermisahigherordercorrectiontothekineticenergy
The third term is the interaction of the electron spin with the magnetic field, so that the complete
expressionfortheZeemaninteractionoftheelectronis
HZ=(B/)B.(l+2s)
Thefactor2isnotquiteexact.Theexpressionis2(1+/2.....)2.0023,where=e2/40hc1/137
isthefinestructureconstant.
Thefourthtermisthespinorbitineteraction.,whichforacentralpotentialV(r)=Ze 2/40rwithZeas
the nuclear charge becomes Ze20l.s/8m2r3 since 00 = 1/c2. In an atom <1/r3> (0.1 nm)3 so the
magnitudeofthespinorbitcouplingis2.5Kforhydrogen(Z=1),60Kfor3delements(Z 25),and
160Kforactinides(Z65).
JS3015 - 2003
38
Inanoncentralpotential,thespinorbitinteractionis(sV).p

Magnetismandrelativity.
Theclassificationofinteractionsaccordingtotheirrelativisticcharacterisbasedonthekineticenergy
E=mc2[1+(v2/c2)]
Theorderofmagnitudeofthevelocityofelectronsinsolidsisc.Expandingtheequationinpowersof
cgives
E=mc2+(1/2)2mc2(1/8)4mc2
Heretherestmassoftheelectron,mc2=511keV;thesecondandthirdterms,whichrepresenttheorder
of magnitude of electrostatic and magnetostatic energies are respectively 13.6 eV and 0.18 meV.
Magneticdipolarinteractionsarethereforeoforder2K.

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39

4.Magnetismoflocalizedelectronsontheatom
Thequantummechanicsofasingleelectroninacentralpotentialleadstoclassificationoftheoneelectronstatesintermsoffour
quantumnumbers.Theindividualelectronsspinandorbitalangularmomentaarecoupledinthemanyelectronion,andspinorbit
couplingoperatestogiveaseriesofenergylevels(multiplets),thelowestofwhichisspecifiedbyHundsrules.Whenplacedina
solid,theionexperiencesacrystalfieldduetothechargeenvironmentwhichmodifiesthespinorbitcouplingandmakeseitherSor
J the good quantum number. In the presence of a magnetic field, the atomic moment is aligned, or equivalently the magnetic
sublevelsaresplitbytheZeemaninteraction.

4.1Thehydrogenicatomandangularmomentum.
z
AhydrogenicatomiscomposedofanucleusofchargeZeattheoriginandan
l e
r
electronatr,,.First,considerasingleelectroninacentralpotentiale=Ze/4e0r
H=(2/2m)Ze2/4e0r

Inpolarcoordinates:

=2/r2+(2/r)/r+1/r2{2/2+cot/+(1/sin2)2/2}
Ze
Theterminparenthesesisl2.Schrdingersequationis H=E
ThewavefunctionmeansthattheprobabilityoffindingtheelectroninasmallvolumedVarr
is*(r)(r)dV.(*isthecomplexconjugateof.
EigenfunctionsoftheSchrdingerequationareoftheform(r,,Rr()
Theangularpart()iswrittenasYlml(,).
ThesphericalharmonicsYlml(,)dependontwointegersl,ml,wherelis0and|ml|l.
exp(iml)whereml=0,1,2.......
Thezcomponentoforbitalangularmomentum,representedbytheoperatorlz=i/,
haseigenvalues<lzml.
()=Plml(cos),aretheassociatedLegendrepolynomialswithl|ml|,
JS3015 - 2003
soml=0,1,2,....l.

40

z
Thesquareoftheorbitalangularmomentuml2haseigenvaluesl(l+1).
Theorbitalangularmomentumhasmagnitudel(l+1)]anditsprojection
alongzcanhaveanyvaluefromlto+l.Thequantitieslzandl2canbe
measuredsimultaneously(theoperatorscommute).Inthevectormodel,
Thetotalangularmomentumisavectorwhichprecessesaroundz.
Sphericalharmonics.

ml
[l(l+1)]

sY00=(1/4)
pY10=)cos

Y11=)sinei

dY20=)(3cos21)
Y21=)sincosei

Y22=)sin2e2i
fY30=)(5cos33cos) Y31=)(5cos21)sinei
Y32=)sin2cose2i Y33=)sin3e3i
TheradialpartR(r)dependsonlandalsoonn,thetotalquantumnumber;n>l;hencel=0,1,......(n
1).
R(r)=Vnl(Zr/na0)exp[(Zr/na0)]
V10=1.Herea0=402/me2=52.9pmisthefirstBohrradius,thebasiclengthscaleinatomicphysics.
Theenergylevelsofthe1electronatomare
E=Zme4/8h202n2=ZR/n2
4

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41

The three quantum numbers n, l, ml denote an orbital, a spatial distribution of electronic charge.
Orbitalsaredenotednx,x=s,p,d,fforl=0,1,2,3.Eachorbitalcanaccommodate
uptotwoelectronswithspinms=1/2.Notwoelectronscanbeinastatewiththesamefourquantum
numbers(Pauliexclusionprinciple).Thehydrogenicorbitalsarelistedinthetable

ml

ms

Noofstates

1s

1/2

2s

1/2

2p

0,1

1/2

3s

1/2

3p

0,1

1/2

3d

0,1,2

1/2

10

4s

1/2

4p

0,1

1/2

4d

0,1,2

1/2

10

4f

0,1,2,3 1/2

14

The Pauli principle states that no two electrons can have the same four quantum numbers. Each
orbitalcanbeoccupiedbyatmosttwoelectronswithoppositespin.
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42

JS3015 - 2003

43

4.2Themanyelectronatom.
Inthemanyelectronatom,termslikee2/40rij,mustbeaddedtotheHamiltonian.Onewayofdealing
with the extra Coulomb interactions is to suppose that each electron sees a different spherical charge
distribution,whichproducesadifferentcentralpotentialforeachone.Thepotentialwithmanyelectrons
isnotasimpleCoulombpotentialwell;thedegeneracyofelectronswithdifferentlisraised.The4sshell,
forexample,isthenlowerinenergythanthe3dshell,whichdefinestheshapeoftheperiodictable.The
quantitiesVI(r)mustbedeterminedselfconsistently(theHartreeFochapproximation)
When several electrons are present on the same atom, at most two of them having opposite spin can
occupythesameorbital(Pauliprinciple).Theirspinandorbitalangularmomentaaddtogiveresultants
1s
2s

2p
MLMS
S=si,MS=msi,L=li,ML=mli.
Consider the sixelectron carbon atom;
1s22s22p2. The 15 states fall into three
groups,orterms.

2
1
1
1

1
0
0
1

ThenotationfortermsistodenoteL=1.

2.3..byS,P,D,.andtoincludethe

spinmultiplicity2S+1asasuperscript.

Theenergysplittingofthetermsisof

order1eV.

2S+1

Inspectroscopy,theenergyunitcm1isused.Handyconversionsare:1eV11605Kand1cm11.44K
JS3015 - 2003

44

Term
1S
3P
1D

0
1
2

0
1
0

(ML,MS)
(0,0)
(1,1)(1,0)(1,1)(0,1)(0,0)(0.1)(1,1)(1,0)(1,1)
(2,1)(2,0)(0,0)(1,0)(2,0)
(2,0)(1,0)

L
Finallyweneedtocouplethespinandorbitalangularmomentum
toformaresultantJ.J=L+S
Hundsrules;Aprescriptionforthelowestenergystate.
Addition of L and S in the vector model
1)
FirstmaximizeSfortheconfiguration
2)
ThenmaximizeLconsistentwiththatS
3)
FinallycoupleLandS;J=LSifshellis<halffull;J=L+Sifshellis>halffull.

Intheexample,S=1,L=1,J=0.Thegroundstateofcarbonis3P0,whichisnonmagnetic(J=0).
Generalnotationformultipletsis2S+1XJwhereX=S,P,D......forL=0,1,2.....
Fe3+
3d5
|
Some examples:
S=5/2

L=0

J=5/2

S5/2

Ni2+
S=1

3d8
L=3

|
J=4

3
F4

Nd3+
S=3/2

4f3
L=6

|
4
J=9/2
I9/2

Dy3+

4f9

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6

45

Variation of L, S, and J for the 3d and 4f series of atoms

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46

4.3Spinorbitcoupling
ThisrelativelyweakrelativisticinteractionisresponsibleforHund'sthirdrule.Inthemultielectron
atom,thespinorbittermintheHamiltoniancanbewrittenas
Hso=L.S
is > 0 for the first half of the 3d or 4f series and < 0 for the second half. It becomes large in
heavyelements.isrelatedtotheoneelectronspinorbitcouplingconstantby=/2Sforthe
firstandsecondhalvesoftheseries.Theresultantangularmomentum(seeabove)is
J=L+S
TheidentityJ2=L2+S2+2L.SisusedtoevaluateHso.TheeigenvaluesofJ2areJ(J+1)h2 etc,
henceL.Scanbecalculated.
4f1
Ce3+
920
Exercise: Calculate the multiplet
splitting in terms of the spin
4f2
Pr3+
540
Spinorbitcouplingconstantsinthe
orbitinteractionforanionwithL=
3dand4fseries
ion
4f3
Nd3+
430

3,S=1/2.
1
3+
5
3+
3d

Ti

124

4f

Sm

350

3d2

Ti2+

88

4f8

Tb3+

-410

3d3

V2+

82

4f9

Dy3+

-550

3d4

Cr2+

85

4f10

Ho3+

-780

3d6

Fe2+

-164

4f11

Er3+

-1170

3d7

Co2+

-272

4f12

Tm3+

-1900

3d8

Ni2+

-493

4f13

Yb3+

-4140
JS3015 - 2003

47

4.4Zeemaninteraction
Themagneticmomentofanionisrepresentedbythetermm=(L+2S)B/
TheZeemanHamiltonianforthemagneticmomentinafieldBappliedalongzism.B
HZ=(B/)B.(L+2S)

The vector model of the atom, including

magnetic moments. First project m onto J. J
thenprecessesaroundz.

S
m
J

Wedefinethegfactorfortheatomorionasthe
ratio of the component of magnetic moment
along J in units of B to the magnitude of the
L
angularmomentuminunitsof.
g=(m.J/B)/(J2/)=m.J/J(J+1)B.e
but
m.J=(B/){(L+2S).(L+S)}
J2=J(J+1)2;
(B/){(L2+3L.S+2S2)}
(B/){(L2+2S2+(3/2)(J2L2S2)}
(B/){((3/2)J2(1/2)L2+(1/2)S2)}
(B/){((3/2)J(J+1)(1/2)L(L+1)+(1/2)S(S+1)}
hence
g=3/2+{S(S+1)L(L+1)}/2J(J+1)
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Jz=MJ

48

Also,fromthevectordiagramitfollowsthatmz/Jz=m.J/J2=gB/.
ThemagneticZeemanenergyisEZ=mzB.Thisis(mZJz)./(JzB)=(gB/)JzB
MJ

-5/2
Hence
EZ=gBMJB
-3/2
J = 5/2

TheeffectofapplyingamagneticfieldonanionwithJ=5/2.

-1/2
1/2
3/2
5/2

Notethemagnitudesoftheenergiesinvolved:Ifg=2.B=9.271024JT1.Thesplittingoftwoadjacent
energylevelsisgBB.ForB=1T,thisisonly21023J,equivalentto1.4K.[kB=1.381023JK1]
The basis of electron spin resonance is to apply a magnetic field to split the energy levels, and then
apply radiation of frequency so that E = h is sufficient to induce transitions between the Zeeman
levels.Sinceh=6.631034Js1,28GHzforresonancein1T.Thisisinthemicrowaverange.
Itispossibletodeducethetotalmomentfromthesusceptibility,whichshouldgivemeff=g[J(J+1)]B.
forfreeions(5.2.2).Themaximumvalueofmzisdeducedfromthesaturationmagnetization.
Generallymeff>mz
For4fionsJisthegoodquantumnumber,butfor3dionsSisthegoodquantumnumber

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49

Energy levels of Co2+ ion, 3d7. Note that the

Zeeman splitting is not to scale.

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50

4.5

Ionsinsolids.

Summarizing,forfreeions;
Filledelectronicshellsarenotmagnetic(thespinsarepaired;m s=1/2)
Onlyunfilledshellsmaypossessamagneticmoment
Themagneticmomentisgivenbym=gBJ,whereJrepresentsthetotalangularmomentum.Fora
givenconfigurationthevaluesofgandJinthegroundstatearegivenbyHundsrules
When the ion is embedded in a solid, the crystal field interaction is important, and the third point is
modified
Orbitalangularmomentumfor3dionsisquenched.ThespinonlymomentismgBS,withg=2.
Magnetocrystalline anisotropy appears, making certain crystallographic axes easy directions of
magnetization.
TheHamiltonianisnow
H=H0+Hso+Hcf+HZ

Typicalmagnitudesofenergyterms(inK)

H0

Hso

Hcf

HZin1T

3d

15104 102103

1104

4f

16105 15103

3102

HsomustbeconsideredbeforeHcf for4fions,andtheconversefor3dions.HenceJisagoodquantum
numberfor4fions,butSisagoodquantumnumberfor3dions.The4felectronsaregenerallylocalized,
and3delectronsarelocalizedinoxidesandotherioniccompounds.
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51

Themostcommoncoordinationfor3dionsis6fold(octahedral)or4fold(tetrahedral).Bothhavecubic
symmetry,ifundistorted

Octahedralandtetrahedralsites.
To demonstrate quenching of orbital angular momentum, we consider the l = 1 states 0,1,1
correspondingtoml=0,1.
0
=
R(r)cos
1
=
R(r)sinexp}
ThefunctionsareeigenstatesinthecentralpotentialV(r)buttheyarenoteigenstatesofHcf.Supposethe
oxygenscanberepresentedbypointchargesqattheircentres,thenfortheoctahedron,
Hcf=Vcf=D(x4+y4+z43y2z23z2x23x2y2)
whereDeq/oa.ButarenoteigenfunctionsofVcf,e.g.?i*VcfjdVij,wherei,j=1,0,1.
Weseeklinearcombinationsthatareeigenfunctions,namely
0= R(r)cos zR(r)=pz
(1/2)(1+1)= R(r)sincos
=xR(r)=px
(1/2)(11)= R(r)sinsin
=yR(r)=py
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52

Notethatthezcomponentofangularmomentum;lz=i/iszeroforthesewavefunctions.Hence
theorbitalangularmomentumisquenched.
Thesameappliesto3dorbitals;theeigenfunctionsthereare
dxy=(1/2)(22)=
R(r)sin2sin2
xyR(r)
dyz=(1/2)(11)=
R(r)sincossin yzR(r)t2gorbitals
dzx=(1/2)(1+1)=
R(r)sincoscos zxR(r)
dx2y2=(1/2)(2+2)=
R(r)sin2cos2
(x2y2)R(r)
egorbitals
d3z2r2=0
=
R(r)(3cos2 (3z2r2)R(r)
The three p-orbitals are degenerate in a
eg
dx2y2,dz2
t2
cubic crystal field, whether octahedral
dxy,dyz,dzx
or tetrahedral, whereas the five d-orbitals
px,py,pz
split into a group of three t2g and a group
e
of two eg orbitals
t2g
dx2y2,dz2
dxy,dyz,dzx
Notation; a or b denote a nondegenerate singleelectron orbital, e a twofold degenerate orbital and t a
threefold degenerate orbital. Capital letters refer to multielectron states. a, A are nondegenerate and
symmetricwithrespecttotheprincipalaxisofsymmetry(thesignofthewavefunctionisunchanged),b.
Bareantisymmetricwithrespecttotheprincipalaxis(thesignofthewavefunctionchanges).Subscripts
g and u indicate whether the wavefunction is symmetric or antisymmetric under inversion. 1 refers to
mirrorplanesparalleltoasymmetryaxis,2referstodiagonalmirrorplanes.
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53

JS3015 - 2003

54

As the site symmetry is reduced, the degeneracy of the oneelectron

energy levels is raised. For example, a tetragonal extension of the
octahedronalongthezaxiswilllowerpzandraisepxandpy.Theeffect
on the dstates is shown below. The degeneracy of the dlevels in
differentsymmetryisshowninthetable.
dx2-y2
dz2

Px,py

dxy

pz

Theeffectofatetragonaldistortionof
octahedralsymmetryonthe
oneelectronenergylevels.
Thesplittingofthe1electronlevels
indifferentsymmetry

dyz,dzx

Cubic Tetragonal Trigonal Rhombohedral

1,2

1,2

1,1,1

2,3

1,1,1,2

1,2,2

1,1,1,1,1

1,3,3

1,1,1,2,2

1,1,1,2,2

1,1,1,1,1,1,1

Asystemwithasingleelectron(orhole)inadegeneratelevelwilltendtodistortspontaneously.The
effect is particularly strong d4 and d9 ions in octahedral symmetry (Mn3+, Cu2+) which can lower their
energy by distorting the crystal environment. This is the JahnTeller effect. If the local strain is , the
energychangeE=A+B2,wherethefirsttermisthecrystalfieldstabilizationenergyandthesecond
termistheincreasedelasticenergy.
JS3015 - 2003

55

5Paramagnetism

Insmallfields,theaverageatomicmomentisproportionaltoappliedmagneticfield,andtheCurielawsusceptibility
C/Tiscalculatedfirstforclassicalmoments,andthenbyquantumstatisticalmechanics.Thecompletemagnetizationcu
isgivenbytheLangevinfunctionortheBrillouinfunctioninthetwocases.Incontrast,thesusceptibilityofametalisv
smallandtempratureindependent.

WestudytheresponseofamagneticmomentmtoanappliedmagneticfieldH.
5.1ClassicalTheory
Langevintheory.Thisistheclassicaltheory.Eachatomhas
asmallmomentm.whichcanadoptanyorientationrelative
totheappliedfieldH=(B/0).Theenergyism.B=0m.H

z
2sin d
H

E()=0mHcos
TheprobabilityP()ofthemomentmakingananglewithz
istheproductofaBoltzmannfactorexp{E(kT}andageometric
factor2sind.HenceP()=2sinexp{E(kT}d
whereisdeterminedbythenormalizationcondition
=P()d()=N,thenumberofmomentsperunitvolume.
m>=mcosPdPd

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56

To evaluate the integrals, let a = cos ; da = sin d and define x = 0mH/kBT which is the
dimensionlessratioofmagnetictothermalenergy.Thisgives
m>=m{cothx1/x}.
The quantity in {} is the Langevin function L(x). At low fields, L(x) x/3. The susceptibility of an
ensembleofNmomentsisr=N<m>/H,hence
r=0Nm2/3kBT
ThisisthefamousCurielaw;itisalsowrittenas r=C/TwhereC=0Nm2/3kB istheCurieconstant.
Units of C are kelvin. At high fields, x >> 1 the magnetization saturates; L(x) 1; the moments are
<m>/m
aligned,<m>=m
1

TheLangevinfunctionL(x).
Theslopeattheoriginis1/3.
0

Langevintheoryisafairapproximationforatomswithlargequantumnumbers(thecorrespondence
principle).Itisalsoappliedtotinyferromagneticparticleswhosedirectionofmagnetizationis
randomizedbythermalexcitation(superparamagnetism).Ferrofluidsarecolloidalsuspensionsof
superparamagneticparticles
JS3015 - 2003

57

5.2Quantumtheory
S=1/2
TheextremequantumlimitisthecaseJ=1/2.UsuallythisariseswhenS=1/2,L=0Thereareonlytwo
energylevelsEi=0gBMSH,whereMS=1/2andtwopossibleorientationsofthemomentrelativeto
theappliedfield.Momentsofthetwostatesaremi=gBMS.Thestatesarealsoknownasspinup(and
spindown().Asingleelectronhass=1/2andg=2,somi=B..
ThepopulationofanenergylevelisgivenbyBoltzmannstatistics;itisproportionaltoexp{E(kT}.
Thethermodynamicaverage<m>isevaluatedfromtheBoltzmannpopulationsofthelevelsEi.
<m>=imiexp{EikT}/Iexp{EikT}
Thedenominatorisanormalizationfactorknownasthepartition
functionZ.Inthepresentcasethereareonlytwotermsinthesums
<m>=[(1/2)gBexp(x)(1/2)gBexp(x)]/[exp(x)+exp(x)]
<m>=mtanh(x)

wherem=(1/2)gB.WhenS=1/2,g=2,thisreducesto
<m>=0tanh(x).Herex=0mH/kBT.Atsmallfields,tanh(x)x,
hence
r=0NB2/kBT
Thisisjustthreetimesaslargeastheclassicalvalue
Manytwolevelsystemsinphysicsaretreatedbyassigning
apseudospinS=1/2
JS3015 - 2003

S=1/2

Ms
1/2

0BH
1/2
z

1/2
g [S(S+1)]B

1/2

58

Generalcase
ThegeneralquantumcasewastreatedbyBrillouin;misgBJ,andxisdefinedasx=0mH/kBT. There
arenow2J+1energylevelsEi=0gBMJH,withmomentmi=gBMJ whereMJ=J.J1,J2,J.The
sumsovertheenergylevelsnowhave2J+1terms.
a)SusceptibilityTocalculatethesusceptibility,wecantakex<<1,becausethesusceptibilityisdefined
astheinitialslopeofthemagnetizationcurve.Weexpandtheexponentialsin(5.6)exp(x)=1+x+..,
<m>=JJgBMJ(1+0gBMJH/kBT)/JJ(1+0gBMJH/kBT)
MJ
5/2
Recall JJ1=2J+1
3/2
JJMJ=0
J=5/2
1/2
J
2
J MJ =J(J+1)(2J+1)/3
1/2
3/2
Hence <m>=0g2B2HJ(J+1)(2J+1)/3(2J+1)kBT
5/2
5/2
TherelativesusceptibilityisN<m>/H,whereNisthe
numberofatoms/m3.
3/2
r=0Ng2B2J(J+1)/3kBT

1/2
1/2

ThisisthegeneralformoftheCurielaw.Againitcanbe
3/2
writtenr=C/TwheretheCurieconstant
5/2
C=0Ng2B2J(J+1)/3kBorC=0Nmeff2/3kBwhere
meff=gBJ(J+1)].AtypicalvalueofCforJ=1,N=8.1028m3is3.5K.
Note that the previous results for the classical limit and S = 1/2 are obtained as thelimits J m=
gBJ)andJ=1/2,g=2.
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59

2S+1

Ion 3d
2+

4+

D3/2
F2
4
F3/2
5
D0
6
S5/2
5
D4
4
F9/2
3
F4
2
D5/2

2
3
3
2
0
2
3
3
2

1/2
1
3/2
2
5/2
2
3/2
1
1/2

3/2
2
3/2
0
5/2
4
9/2
4
5/2

4/5
2/3
2/5
2
3/2
4/3
5/4
6/5

Ti , V
(3d )
2+
3+
2
Ti , V
(3d )
2+
3+
3
V , Cr
(3d )
2+
3+
4
Cr , Mn (3d )
2+
3+
5
Mn , Fe (3d )
2+
3+
6
Fe , Co (3d )
2+
3+
7
Co , Ni (3d )
2+
8
Ni
(3d )
2+
9
Cu
(3d )

Ion 4f

LJ

LJ

2S+1

m eff g J (J 1) m s 2 S(S 1)

( B )

( B )

1.549
1.633
0.775
5.916
6.708
6.633
5.590
3.550

1.73
2.83
3.87
4.90
5.92
4.90
3.87
2.83
1.73

m0=gJ
(B)

Ce3+ (4f1)

(B)

5/2

6/7

2.14

2.54

2.5

H4

4/5

3.20

3.58

3.5

I9/2

3/2

9/2

8/11

3.27

3.62

3.4

I4

3/5

2.40

2.68

H5/2

5/2

5/2

2/7

0.71

0.85

1.7

F0

0.00

0.00

3.4

S7/2

7/2

7/2

7.00

7.94

8.9

F6

3/2

9.00

9.72

9.8

H15/2

5/2

15/2

4/3

10.00

10.65

10.6

I8

5/4

10.00

10.61

10.4

I15/2

3/2

15/2

6/5

9.00

9.58

9.5

H6

7/6

7.00

7.56

7.6

F7/2

1/2

7/2

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8/7 - 2003 4.00

4.53

4.5

Pm3+(4f4)
6

Eu3+ (4f6)

7
8

Tb3+ (4f8)

7
6

Ho3+ (4f10)
Er3+ (4f11)

meff

1/2

Nd3+ (4f3)

Dy3+ (4f9)

1.7
2.8
3.8
4.9
5.9
5.4
4.8
3.2
1.9

Gd3+ (4f7)

(B)

( B )

F5/2

P3+ (4f2)

Sm3+(4f5)

meff=g(J(J+1)

m eff *

Tm3+ (4f12)

Yb3+ (4f13)

60

b)Magnetization
Tocalculatethecompletemagnetizationcurve,sety=0gBH/kBT,
then
<m>=gB/y[lnJJexp{MJy}]
[d(lnz)/dy=(1/z)dz/dy]
Thesumovertheenergylevelsmustbeevaluated;itcanbewrittenas
exp(Jy){1+r+r2+.........r2J}
wherer=exp{y}
Thesumofageometricprogression(1+r+r2+....+rn)=(rn+11)/(r1)
JJexp{MJy}=(exp{(2J+1)y}1)exp{Jy}/(exp{y}1)
multiplytopandbottombyexp{y/2}
=[sinh(2J+1)y/2]/[sinhy/2]
<m>=gB(/y)ln{[sinh(2J+1)y/2]/[sinhy/2]}
=gB/2{(2J+1)coth(2J+1)y/2cothy/2}
settingx=Jy,weobtain<m>=mBJ(x)
1.0
wheretheBrillouinfunctionBJ(x)=
{(2J+1)/2J}coth(2J+1)x/2J(1/2J)coth(x/2J). 0.81/2
Again,thisreducestothepreviousequations
2
inthelimitsJm=gBJ)andJ=1/2,g=2. 0.6
,

0.4
0.2
ComparisonoftheLangevinfunctionandthe
BrillouinfunctionsforJ=1/2andJ=2.

0
0

2
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x
61

Reducedmagnetizationcurvesforthreeparamagneticsalts,withBrillouintheorypredictions

Thetheoryoflocalizedmagnetismgivesagoodaccountofmagneticallydilute3dand4fsaltswherethe
magneticmomentsdonotinteractwitheachother.Exceptinlargefieldsorverylowtemperatures,the
M(H)responseislinear.Fields>100Twouldbeneededtoapproachsaturationatroomtemperature.
Theexcellenceofthetheoryisillustratedbythefactthatdataforquitedifferenttemperaturessuperpose
onasingleBrillouincurveplottedasafunctionofxH/T
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62

6.Ferromagnetism.
FerromagnetismandtheCurietemperaturewereexplainedbyWeissintermsofahugeinternalfield,themolecular
fieldproportionaltothemagnetization.Nosuchmagneticfieldreallyexists,butitisawayofrepresentingtheeffect
of quantum mechanics on the Coulomb interaction. The Weiss model can be applied to localized or delocalized
electrons. Heisenberg represented the interaction of two localized spins S1 and S2 by the Hamiltonian H 2JS1.S2.
When J > 0, the exchange is ferromagnetic, leading to ferromagnetic order but when J < 0, the exchange is
antiferromagnetic, leading to magnetic order that depends on lattice topology. Physical phenomena associated with
ferromagnetismarethehysteresisloopandmagneticanisotropy.Becauseofthedemagnetizingfield,thelowestenergy
stateofaferromagnetisusuallyamultidomainstatewithnonetmagnetization.Thedomainsareseparatedbydomain
walls.Methodsofmeasuringmagnetizationarediscussed.

Thecharacteristicfeaturesofferromagneticorderarespontaneousmagnetisation Ms duetospontaneous
alignment of the atomic magnetic moments, which disappears on heating above a critical temperature
known as the Curie point. The magnetization tends to lie along certain easy directions determined by
crystalstructureorsampleshape.
6.1
Meanfieldtheory
Weiss(1907)supposedthatinadditiontoanyexternallyappliedfieldH,thereisaninternalmolecular
fieldinaferromagnetproportionaltoitsmagnetization.
Hi=nWM
Hi mustbeimmenseinaferromagnetlikeirontobeabletoinduceasignificantfractionofsaturationat
room temperature; nW 100. The origin of these huge fields remained a mystery until Heisenberg
introducedtheideaoftheexchangeinteractionin1928.
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63

Magnetization is given by the Brillouin function, <m> = mBJ(x) where now x = 0mHi/kBT. The
spontaneousmagnetizationatnonzerotemperatureMs=N<m>andM0=Nm.Inzeroexternalfield,we
have
Ms/M0=BJ(x)
(1)
ButalsobyeliminatingHifromtheexpressionsforHiandx,
Ms/M0=(NkBT/0M02nW)x
whichcanberewrittenintermsoftheCurieconstantC
Ms/M0=[T(J+1)/3CJnW]x
(2)
Thesimultaneoussolutionof(1)and(2)isfoundgraphically,ortheycanbesolvednumerically.
<m>/m
1
T > TC

T = TC

T < TC

Graphical solution of (1) and (2) for J = 1/2 to find the spontaneous magnetization M s when T < TC. Eq. (2) is also
plottedforT=TCandT>TC.
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64

AttheCurietemperature,theslopeof(2)isequaltotheslopeattheoriginoftheBrillouinfunction
Forsmallx.
BJ(x)[(J+1)/3J]x+...
hence

TC=nWC

wheretheCurieconstant
C=0Ng2B2J(J+1)/3kB.
AtypicalvalueofTCisafewhundredKelvin.Inpractice,TCisusedtodeterminenW.
InthecaseofGd,TC=292K,J=S=7/2;g=2;N=3.0x1028m3;henceC=4.9K,nW=59.Thevalue
ofM0=NgBJis1.95MAm1.Hence0Hi=144T.

Thespontaneousmagnetizationfornickel,together
withthetheoreticalcurveforS=1/2fromthemean
fieldtheory.Thetheoreticalcurveisscaledtogive
correctvaluesateitherend.
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65

T> TCTheparamagneticsusceptibilityaboveTC isobtainedfromthelinearterm BJ(x) [(J+1)/3J]x

withx=0m(nWM+H)/kBT.TheresultistheCurieWeisslaw
=C/(Tp)
where
p=TC=0nWNg2B2J(J+1)/3kB
Inthistheory,theparamagneticCurietemperaturepisequaltotheCurietemperatureTC,whichiswhere
thesusceptibilitydiverges.

1/

The Curielaw suceptibility of a paramagnet (left) compared with the CurieWeiss susceptibility of a ferromagnet
(right).

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66

6.2ExchangeInteractions.
What is the origin of the effective magnetic fields of 100 tesla or more which are responsible for
ferromagnetism?Theyarenotduetotheatomicmagneticdipoles.Thefieldatdistancerduetoadipole
mis
Bdip=(0m/4r3)[2coser+sine].
TheorderofmagnitudeofBdip=0Hdipis0m/4r3;takingm=1Bandr=0.1nmgivesBdip=4.107x
9.27. 1024/ 4 1030 1 tesla. Summing all the contributions of the neighbours on a lattice does not
changethisorderofmagnitude;infactthedipolesumforacubiclatticeisexactlyzero!
The origin of the internal field Hiis the exchange interaction, which reflects the electrostatic Coulomb
repulsionofelectronsonneighbouringatomsandthePauliprinciple,whichforbidstwoelectronsfrom
enteringthesamequantumstate.Thereisanenergydifferencebetweentheandconfigurationsfor
the two atoms. Interatomic exchange is one or two orders of magnitude weaker than the intraatomic
exchangewhichleadstoHundsfirstrule.
The Pauli principle requires the total wave function of two electrons 1,2 to be antisymmetric on
exchangingtwoelectrons
(1,2)=(2,1)
The total wavefunction is the product of functions of space and spin coordinates r1,r2) and (s, s2),
each of which must be either symmetric or antisymmetric. This follows because the electrons are
indistinguishable particles, and the number in a small volume dV can be written as 1,2)dV =
2,1)dV,hence1,2)=2,1).
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67

The simple example of the hydrogen molecule H2 with two atoms a,b with two electrons 1,2 in
hydrogenic1sorbitalsi givestheideaofthephysicsofexchange.Therearetwomolecularorbits,one
spatiallysymmetricS,theotherspatiallyantisymmetricA.
S1,2)=(1/2)(a1b2+a2b1);
A1,2)=(1/2)(a1b2a2b1)

S=0

S=1

ThespatiallysymmetricandantisymmetricwavefunctionsforH2.

Thesymmetricandantisymmetricspinfunctionsarethespintripletandspinsingletstates
S=|2>;(1/)[|2>+|2>];|2>.
S=1;MS=1,0,1
A=(1/)[|2>|2>]

S=0;MS=0

According to Pauli, the symmetric space function must multiply the antisymmetric spin function, and
viceversa.Hencethetotalwavefunctionsare
I=S(1,2)A(1,2);II=A(1,2)S(1,2)
TheenergylevelscanbeevaluatedfromtheHamiltonianH(r1,r2)
EI,II=S,A(r1,r2)H(r1,r2)S,A(r1,r2)dr1dr2
2
2
2
JS3015,r
- 2003
Withnointeractionoftheelectronsonatomsaandb,H(r
1
2)isjustH0=( /2m){1 +1 }+V1+V2.68

ThetwoenergylevelsEI,E,IIaredegenerate,withenergyE0.However,iftheelectonsinteractviaaterm
H = e2/40r122, we find that the perturbed energy levels are EI = E0+2J, EII = E0 2J. The exchange
integralis
J=a1*b2*(r)H(r12)a2b2dr1dr2
andtheseparation(EIIEI)is4J.FortheH2molecule,EIislieslowerthanEII,thebondingorbitalsinglet
stateliesbelowtheantibondingorbitaltripletstateJisnegative.Thetendencyforelectronstopairoffin
bondswithoppositespiniseverywhereevidentinchemistry;thesearethecovalentinteractions.Wewrite

thespindependentenergyintheform
E=2(J/2)s1.s2
wheretheoperators1.s2is1/2[(s1+s2)2s12s22].According
towhetherS=s1+s2 is0or1,theeigenvaluesare(3/4)2
or (1/4)2.The splitting betweeen the singletstate (I)
andthetripletstate(II)isthenJ.

J'

Energysplittingbetweenthesingletand
tripletstatesforhydrogen.

Heisenberggeneralized(6.14)tomanyelectronatomicspinsS1andS2,writinghisfamousHamiltonian
H=2JS1.S2
Where2isabsorbedintotheJ.J>0indicatesaferromagneticinteraction(favouringalignment.J<
0 indicates an antiferromagnetic interaction (favouring alignment. When there is a lattice, the
Hamiltonian is generalized to a sum over all pairs i.j, 2i>jJijSi.Sj. This is simplified to a sum with a
singleexchangeconstantJifonlynearestneighbourinteractionscount.
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69

The Heisenberg exchange constant J can be related to the Weiss constant nW in the molecular field
theory.SupposethemomentgBSiinteractswithaneffectivefieldHi=nWM=nWNgBS,andthatinthe
HeisenbergmodelonlythenearestneighoursofSihaveanappreciableinteractionwithit.Thenthesite
Hamiltonianis
Hi=2(jJSj).SiHigBSi
ThemolecularfieldapproximationamountstoneglectingthelocalcorrelationsbetweenSiandSj.IfZis
thenumberofnearestneighboursinthesum,thenJ=nWNg2B2/2Z.Hence,fromtheexpressionforTCin
termsoftheWeissconstantnW
TC=2ZJJ(J+1)/3kB
TakingtheexampleofGdagain,whereTC=292K,J=7/2,Z=12,wefindJ/kB=2.3K.
Exchangeinmetals
The Heisenberg theory describes the exchange coupling of electrons in localized orbitals. It does not
apply in metals, where there are partlyfilled bands. Generally, the energy of any electronic system is
lowered as the wavefunctionsspreadout.Thisfollows fromthe uncertaintyprinciple px h.When
manymoreorlessdelocalizedelectronsarepresentindifferentorbitals,thecalculationofexchangeisa
delicatematter.Energiesinvolvedareonly 0.01eV,comparedwithbandwidthsWoforder110eV.
Therearecompetingexchangemechanismswithdifferentsignsofcoupling.
The principal exchange mechanism in ferromagnetic and antiferromagnetic metals involves direct
overlapofthepartlylocalizedatomicorbitalsofadjacentatoms.Otherexchangemechanismsinvolvethe
interactionoflocalizedanddelocalizedmomentsinthemetal.
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70

In3dmetals,theelectronsaredescribedbyextendedwavefunctionsandaspinpolarizedlocaldensityof
states,introducedin5.3.ThebandwidthinthetightbindingmodelisW=2ZtwhereZisthenumber
ofnearestneighboursandtisthetransferintegral.In3dmetalst 0.1eV.Inaroughlyhalffilledband
the exchange is antiferromagnetic, whereas in a nearlyfilled or nearly empty band it tends to be
ferromagnetic. The sign of the exchange depends first on band occupancy, then on the interatomic
spacing,withferromagneticexchangefavouredatlargerspacing.

No
Yes

Yes

Yes

Electrondelocalizationindbandswhicharehalffull,oralmostemptyoralmostfull.

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71

Stonercriterion.
Ferromagnetic exchange in metals does not necessarily lead to spontaneous ferromagnetic order. The
Paulisusceptibilitymustexceedacertainthreshold.Ferromagneticmetalshaveanexceptionallylarge
density of states at the Fermi level N(EF). Stoner applied Weisss molecular field idea to the free
electronmodel.
Hi=nSM
HerenSisthemolecularfieldconstant;Thebare
Paulisusceptibilityp=M/(H+nSM)isenhanced:
=M/H=p/(1nSp)
Hencethesusceptibilitydivergeswhen
nSp>1.
ThevalueofnSisabout10,000in3dmetals.
ThePaulisusceptibility(3.4)isproportional ComparisionofN(EF)with1/Iformetallicelements.
tothedensityofstatesN(EF).Onlymetalswith
a large N(EF) can order ferromagnetically. A big peak in the density of states at the Fermi level is
needed.Thisiswhythelate3delementsFe,Co,Niareferromagnetic,buttheearly3dor4delements
Ti,V,Crarenot.ElementsinthemiddleoftheseriesCr,Vareantiferromagneticbecausethe3dband
isapproximatelyhalffull.WhentheStonercriterionissatisfied,theandbandssplitspontaneously.
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72

6.3Ferromagneticdomains
Havingdevelopedhismolecularfieldtheory,Weisspostulatedthatthereasonwhymostlumpsofiron,
for example, do not appear ferromagnetic is because they contain many ferromagnetic domains
magnetized in different directions. The reason why domains form is to reduce the magnetostatic self
energyasfaraspossible.ThisselfenergyEmscanbewrittenintwoequivalentforms
Ems = (1/2)all

H2dV

space 0

or

Ems = (1/2)magnetM.BdV

ThevalueofHinsidethemagnetisthedemagnetizingfield Hd=NM,whereNisthedemagnetizing
factor.Hence
Ems=(1/2)0NM2V
Reductionofthedemagnetizingenergyofaferromagnetbysplittingupintodomains.ThevaluesofEmsare
approximately0.10,0.05and0.02inunitsof0M2V

Theparticulardomainstructureadoptedbyapieceofferromagneticmaterialistheresultofminimizing
thetotalenergy,whichinthesumoffourterms
Etot=Ems+Eex+Ea+EZ
TheexchangeenergyEexisthesumof(6.15)overallpairsofatomsinthesample.Eaistheanisotropy
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energydiscusednext.E istheenergyinanexternalfield.

73

Somewaysofvisualizingdomains:
Bitterpattern(spreadferrofluidonthesurface)[dependsonstrayfield]
Atomicforcemicroscopewithamagnetictip[dependsonstrayfield]
MagnetoopticKerreffect[dependsonMinthesurfaceregion]
Lorentz(transmissionelectron)microscopy[dependsonBinathinfoil]

Bitter method (left) and MFM (right)

Domainpatternonthesurfaceofanickelcrystalreveled
bytheBittermethod.
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74

Anisotropy
The tendency for the ferromagnetic axis of a domain to lie along some fixed direction(s) in a sample
known as the easy axis is the phenomenon of magnetic anisotropy. Strong easyaxis anisotropy is a
prerequisiteforhardmagnetism.Nearzeroanisotropyisneededforsoftmagnets.
Generally, the tendency for magnetization to lie along some easy axis is represented by an energy
expressionofwhichtheleadingtermis
Ea=K1sin2
whereistheanglebetweenMandtheanisotropyaxis.
The anisotropy constant K1 depends on temperature, and goes to zero at TC. Units are J m3. Values
typicallyrangefrom102to106Jm3.
Mostcommonsourceofanisotropyismagnetocrystallineanisotropy,wherethemagnetizationprocessis
differentalongdifferentcrystallographicdirections.Thisisrelatedtospinorbitcoupling.Theexpression
Ea=K1sin2isvalidforuniaxialcrystalstructures(hexagonal,tetragonal,trigonal).Incubicsymmetry,a
differentexpressionisnecessarytoreflectthesymmetryofthecubiccrystal.Itis
Eacubic=K1c(1222+2232+3212)
where1,2and3arethedirectioncosinesofthemagnetizationdirectionwithrespecttothecoordinate
axes.However,thisexpressionreducestoK1sin2inthelimitofsmalldeviationsfromaneasyaxis.
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75

Themagnetizationcurveandhysteresisloop

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76

Starting from the thermallydemagnetized state, the following magnetization processes are involved
aroundthehysteresiscurve
12
3
4
56

Reversiblewallmotion
irreversiblewallmotion
coherentrotation
nucleation,irreversiblewallmotion.

Inbulkmaterialitispracticallyimpossible
tocalculatethehysteresisandcoercivity.
Onecasewhereitispossibleisinvery
Smallsingledomainparticleswhere
themagnetizationreversescoherently

Mr

Hc

Thefirsttwoquadrantsofthehysteresisloop

TheenergylossoncyclingthetheM(H)loopisloop0HdM.Forminimumlossesinacapplicationsthe
coercivitynustbeaslowaspossible.
Theotherextremeisneededforapermanentmagnet,wherethehysteresisloopshouldbebroadtoavoid
selfdemagnetizationinthedemagnetizingfieldNM.Ifthemagnetistoremainfullymagnetizedno
matterwhatshapeitis,itshouldhaveasquareloopwithHc>M
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Domainwalls
We now focus on the magnetic structure of the region separating two oppositelymagnetized domains.
This180domainwallisknownasaBlochwall.ThestructureisobtainedbyminimizingtheenergyEtot
=Ems+Eex+Ea.Wegiveanapproximatetreatmentwhichillustratesthephysics.
GrantedweneedtocreateawalltoreduceEms,weseekacompromisebetweenawidewall,whichwould
minimizeEexandanarrowonewhichwouldminimizeEa.Supposewehaveaferromagnetwiththesites
onacubiclatticewithsidea,andsupposealsothatthemagnetizationturnsbyananglefromonesiteto
thenextacrossthewall,asshowninthefigure.
A180Blochwallbetweenoppositelymagnetizeddomains
inasamplewithuniaxialanisotropy.

Thewallwidthwisrelatedtoaand,w=a/
Exchangeenergyforaneighbouringpairofspinsis
2JSi.Sj.=2jS2cos2jS2(12/2+....)
TheextraenergyduetomisalignmentisJS22.
Foralineofspinsacrossthewall,thisisJS2
andperunitareaofwall
Eex=JS2a2
Ifthisweretheonlyterm,wouldbeverysmall,
w.Butthespinsinthewallarepointing
awayfromtheeasyaxis.Theanisotropycostis
about(1/2)K1a3perspinorperunitarea,

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Thewallenergywall=Eex+Eaismimimumwithrespecttowhen
Ew/=JS2/a2(1/2)K1a/2=0.
2=(1/2)K1a3/JS2
w=(2JS2/K1a)
w=(2K1JS2/a)
Takingtheexampleofcobalt,K1=500kJm3,J=S1,andusingTC=1390KandZ=12todeduce
JfromtheexpressionTC=2ZJJ(J+1)/3kBgivesJ=1.21021 J.a 0.2nm;hence w15nm,about75
atomicspacings;w=8mJm2.
Domainwallpinning
ThedomainwallactslikeanelasticmembranewithenergywJm2.Itwillbestronglypinnedatdefects,
especiallyplanardefects,withdifferentJorK1tothebulkifthesedefectshavedimensioncomparable
tothedomainwallwidthw.Weakerpinningoccurswhentherearemanydefectsdistributedthroughout
thewallwidth.Generally,thereisalwayssomedistributionofdefectsinany
sampleofmagneticmaterial.Supposetheenergyofthesystemdependsjust
onthewallpositionx,andappliedfieldH,wheref(x)representstheeffects
x
ofthepinningsites
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Weshowhowahysteresisloopresultsfromtheenergylandscapewithseveralminimaduetopinning.At
local energy minimum df(x)/dx = 20MH. As the wall jumps from points with the same df(x)/dx on
increasingfield,themagnetizationchangesdiscontinuouslyinaBarkhausenjump.Thehysteresisloop
ofamacroscopicsampleconsistsofmanysuchjumps.
f(x)
3
5
2
6

Mx

a)

5
x

df/dx
3

2
4

1
6

2
H

0 Ms H

c)

b)

a) Energyasafunctionofwallposition.b)Theequilibriumconditiondf(x)/dx=20MHc)ahysteresisloopdueto
fieldcycling.
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Singledomainparticles.
When ferromagnetic particles are no bigger than a few tens of nanometers, it does not pay to form a
domainwall.Theenergygainisoforder(1/2)0M2V 0M2r3,whereasthecostofformingthewallis
wr2.Whentheparticleradiusrissufficientlysmall,thelatteroutweighstheformer.Again,whenthe
particleisverysmall,magnetizationreversaltakesplacebycoherentrotationofthemagneticmomentm.

IfanexternalfieldHisappliedatanangletotheeasydirection,andthemagnetizationisat
anangletotheeasydirection,theenergyisEtot=Ems+Ea+EZ thesumofmagnetostatic,anisotropy
andZeemanterms.ThefirsttwoarerepresentedbyatermKusin2,hence
m

Etot=KuVsin mHcos()
2

Theenergycanbeminimized,andthehysteresisloopcalculated
M
M
numericallyforageneralangle.ThisistheStonerWohlfarthmodel.

Asingledomainparticlewherethe
magnetizationrotatescoherently.

Twospecialcasesofgreatinterest:are=0and=/2.Inthefirstcase=0or,andasquareloopis
observedwithaflipfrom=0to=atHc=2Ku/M,(M=m/V).Thesesquareloopsarevaluablefor
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6.4Magneticmeasurements
Methods of measuring magnetization, and hence susceptibility or hysteresis, of magnetic materials
dependeitherontheforceonamagneticmomentinanonuniformfieldF=m.B,oronFaradayslaw
d/dt,whereisthefluxthreadingacircuitandistheinducedemf.Weconsiderthreeexamples:
Forcemethod(Faradaybalance)
Consideringonecomponentoftheforceequation;(misconstant)
Fz=(mxx/z+myy/z+mzz/z)
Ifthefieldisinthexdirection,Fz=mxx/z.Thefieldgradientmaybeproducedusingshapedpole
pieces,orbyspecialfieldgradientcoils.Thegradientiscalibratedwithasampleofknownmagnetization
ofsusceptibility.Sensitivitymaybeimprovedbyapplyinganalternatingcurrenttothegradientcoils,and
usinglockindetection.
Extractionmethod.
Herethesampleisfirstlocatedinapickupcoilinthefield,andthenremovedtoadistantpoint.Anemf
isinducedinthecoil,and
dt=
Thefluxproducedbythedipolemisproportionaltoitsmagnetization.ASQUIDdetectorcanbeused
11
toachievegreatsensitivityinthemeasurementof.Sensitivityof10
Am2inmisthenachievable.
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Vibratingsamplemagnetometer(Fonermagnetometer)
Thisisanacvariantoftheextractionmethod.Thesamplevibrateswithanamplitudeofafewhundred
microns at about 100 Hz, and an alternating voltage is induced in pickup coils. A reference signal is
generatedinanotherpickupcoilorwithacapacitor,andbothsignalandreferencearefedintoalockin
amplifier.Typicalsensitivityis108Am2.

Methodofmeasuringmagnetizationorsusceptibility.a)Faradaybalance,b)extractionmagnetometerandc)Vibrating
samplemagnetometer

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Dataonsomeferromagnets

material

Fe
Co
Ni
Fe65Co35*
Ni80Fe20
Gd
CrO2

(kg/m3)
7874
8836
8902
8110
8715
7886
4870

TC
(K)
1044
1390
628
1240
843
292
396

0M(290K)
(T)
2.15
1.81
0.62
2.34
1.04
0.8
0.50

m0
( B/formula)
2.2
1.7
0.6
2.5
1.1
7.0
2.0

K1
(kJ/m3)
50
530
5
40
<1
20

*permendurpermalloy

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7MiscellaneousTopics
Othertypesofmagneticorderarisingfromantiferomagneticinteractionsareantiferromagnetism,whereM s=0,and
ferrimagnetism, where there are unequal sublattices, and M 0. These cases are treated by an extension of the
molecular field theory to two sublatices. Various types of noncollinear structures arise from competing interactions,
especially in noncrystalline soilds. The elementary excitations from the magnetic ground state are spin waves
(magnons)whicharedescribedbyadispersionrelationE=Dswq2intheferromagneticcaase.Neutronscatteringisa
powerful general method for determining both magnetic structures (magnetic Bragg scattering) and for measuring
magneticexcitations(magneticinelasticscattering)

In the last chapter, we discussed ferromagnetic order, which arises from ferromagnetic exchange
interactions J > 0. In the first two sections here we consider magnetic order which can arise from
antiferromagneticexchangeinteractionsJ<0.
7.1Antiferromagnetism
Inmanystructures,theatomscanbeassignedtotwoequalsublatticesAandB.Thesematerialsmay
havetwooppositelydirectedmagneticsublatticesMAandMB;MA=MB.TwoWeisscoefficientsnWand
nWrepresenttheinterandintrasublatticeinteractions.UsuallynWisnegative.
MA
MB
HAi=nWMA+nWMB+H
HBi=nWMB+nWMA+H

ThenetmagnetizationM=MA+MBiszerowhenH=0.Themagnetizationofeachsublatticeis
representedbyaBrillouinfunction,andeachfallstozeroatacriticaltemperature,theNeltemperatute
TN.Thesublatticemagnetization<M>=M0BJ(x)where=A,Bandx=0mH/kBT,
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M/M0
TN
T

Sublatticemagnetizationofanantiferromgnet.TNistheNeltemperature

AboveTN,M=rHiwhere=C/TwithC=0(N/2)meff2/3kB.HereN/2isthenumberofatomsperm3
ofeachsublattice.Hence
MA=(C/T)(nWMA+nWMB+H)
MB=(C/T)(nWMA+nWMB+H)
Theconditionfortheappearanceofspontaneoussublattocemagnetizationisthattheseequationshavea
nonzerosolutioninzeroappliedfield.Thedeterminantofthecoefficientsiszero,hence[(C/T)nW1]2
[(C/T)nW]2=0,whichyields
TN=C(nWnW)
TocalculatethesusceptibilityaboveTNweevaluater=(MA+MB)/H.AddingtheequationsforMA and
MB,wefindtheCurieWeisslaw
r=C/(Tp)
whereC=2Candp=C(nW+nW).Inthetwosublatticemodel,wecanthereforeevaluatebothn W
andnWfromTNandp.Sincenw<0,p<TN,anditisusuallynegative.Normally1/
risplottedversus
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Paramagnet

Comparisonofthesusceptibilityofa
paramagnet,aferromagnetandan
antiferromagnet.

Ferromagnet

TC

Antiferromagnet

TN

The antiferromagnetic axis along which the sublattice magnetizations lie is determined by
magnetocrystallineanisotropy,andtheresponsebelowTNdependsonthedirectionofHrelativetothis
axis.
MA

MA

Calculationofthesusceptibilityofanantiferromagnet
belowTN.Ina)thedashedlinesshowtheconfiguration
afteraspinflop.

a)||

MB

b)

MB

Hb

Ifasmallfieldisappliedparalleltotheaxis,wecancalculate ||byexpandingtheBrillouinfunctions
about x0, their arguments in zero applied field. For simplicity we take nW = 0, and the result for || =
[MA(H)+MB(H)]/His
||=Nm2BJ(x0)/[kBT+NnWm2BJ(x0)]
Thisrisesfrom0atT=0toC/(Tp)atTN,whereBJ(0)=(J+1)/3J.x0is0mnWM/kBT,whereMisthe
sublatticemagnetizationinzerofield
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Theperpendicularsusceptibilitycanbecalculatedassumingthesublatticesarecantedbyasmallangle
,asinFig7.3.Inequilibriumthetorqueoneachoneiszero,henceM H=MnWMsin2.SinceM=
2Msin,
=1/nW
TheperpendicularsusceptibilityisthereforeconstantandindependentoftemperatureuptoT N.Fora
powder,theaverageis(1/3)||+(2/3),or2/3nWatlowtemperature.

Parallelandperpendicularsusceptibilityofanantiferromagnet.

Since>||forallT<TN,wemightexpectthatanantiferromagnetwillalwaysadoptthetraansverse,
flopped configuration. That it doesnt is due to magneto crystalline anisotropy, represented by an
effectiveanisotropyfieldHK,whichactsoneachsublatticealongtheantiferromagneticaxis.WhenHis
applied parallel to M the spin flop occurs when the energies of the parallel and perpendicular
configurationsareequal;
2MaHK(1/2)||Hsf2=(1/2)Hsf2
Hsf=[4MHK/(||]1/2
When T << TN, this reduces to Hsf = 2(HkHi). Orders of magnitude for the anisotropy field and the
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88
molecularfieldare1Tand100T,respectively,henceH
isoforder10T.

7.2Ferrimagnets.
Aferrimagnetmayberegardedasanantiferromagnetwithtwounequalsublattices.
An example is yttriumiron garnet (YIG) Y3Fe5O12. The ferric iron in YIG occupies two different
crystallographic sites, one (16a) octahedrally coordinated by oxygen, the other (24d) tetrahedrally
coordinated.Neighbouringsitesshareacommonoxygenligand,andthereisastrongantiferromagnetic
adinteraction.Theferrimagneticconfigurationis

a
d
leadingtoamomentof5B/formulaatT=0,duetoasingleuncompensated3d5ionperformulaunit.
Ferrimagnets have two unequal and oppositelydirected magnetic sublattices MA and MB; |MA| |MB|.
ThenetmagnetizationM=MA+MBisnonzero.ThreeWeisscoefficientsnAAandnBB andnAB represent
theinterandintrasublatticeinteractions.TheessentialinteractionnABisnegative
HAi=nAAMA+nABMB+H
HBi=nABMA+nBBMB+H

whenH=0.ThemagnetizationofeachsublatticeisrepresentedbyaBrillouinfunction,andeachfalls
to zero at a critical temperature, the ferrimagnetic Nel temperatute TN. The sublattice magnetization
<M>=M0BJ(x)where=A,Bandx=0mH/kJS3015
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BT,
89

M
MA

MA

Sublatticemagnetizationofanferrimagnet.
TNistheferrimagneticNeltemperature.
Ontheleft,|nAB|>>|nAA|,|nBB|;ontheright,
|nBB|>>|nAB|,|nAA|.Tcompisthe
compensationtemperature.

M
TN

T comp

T
MB

TN
T

MB

AboveTN,M=Hiwhere=C/TwithC=0Nmeff2/3kB.HereNisthenumberofatomsperm3on
eachsublattice.Hence
MA=(CA/T)(nAAMA+nABMB+H)

MB=(CB/T)(nAMMA+nBBMB+H)
Theconditionfortheappearanceofspontaneoussublatticemagnetizationisthattheseequationshavea
nonzerosolutioninzeroappliedfield.Thedeterminantofthecoefficientsiszero,hence[(CA/T)nAA 1]
[(CB/T)nBB1](CACB/T2)nAB2=0,whichyields
TN=(1/2)[(CAnAA+CBnBB)[(CAnAACBnBB)2+4CACBnAB2]
TheexpressionforthesusceptibilityaboveTNisobtained,
1/=(TC+CB)C/(T)
whereC=CACBnAB2/(CA+CB)[CA(1+nAA)CB(1+nBB)]2,=CACBnAB/(CA+CB)[nAACA/CBnBBCB/CA
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2]and=CACBnAB/(CA+CB)[nAA+nBB+2]
90

Exercise:DeriveEq7.11.GiveexpressionsforTNandwhennAA=nBB=0.
Thisistheequationofanhyperbola.

TN

InversesusceptibilityofaferrimagnetaboveitsNelpointTN

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7.3Otherformsofmagneticorder
Various other forms of magnetic order can arise in solids. When
ferromagneticandantiferromagneticinteractionscompete,andcannotall
be satisfied simultaneously, the system is said to be frustrated. A
noncolinear spin structure may then arise, such as a helimagnetic
structure where there are ferromagnetic planes, but the ferromagnetic
axisturnsbyananglefromoneplanetothenext.

Ahelimagnet

Frustration may also arise with purely antiferromagnetic interactions,

whenthereareoddmemberedrings.Someexamplesareshownbelow.

Indisorderedandamorphoussolids,frustratedantiferromagneticinteractions,or
competingferromagneticandantiferromagneticinteractionsmaygiverisetospin
freezinginrandomdirections.Suchmaterialsareknownasspinglasses.
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A spin glass
92

Spinwaves
The exchange energy in the ferromagnetic ground state is 2ZJS2 per site. Elementary excitations
from the ferromagnetic ground state are spin waves, illustrated below. These extended spin
deviations are also known as magnons by analogy with phonons, the quantized lattice waves. A
singlelocalizedspinreversalcosts8JS2 (2J)forS=1/2,whichisgreaterthankBTC
forachain.TC=2ZS(S+1)/3(forJ=S=1/2,Z=2).Suchexpensiveexcitationscannotoccuratlow
temperature;insteadtheatomsallsharethereversal,withperiodicoscillationofspinorientation.

Illustrationofaspinwave.

Inonedimension,therelationbetweenthefrequencyandwavevectorofawavelikeexcitationof
thespinsystemcanbecalculatedclassically
hq=4JS(1cosqa)
E
Inthelimitofsmallwavevectors,thedispersionrelationbecomes
EqDswq2
whereEq=hq,Dsw=2JSa2;aistheinteratomicspacing.
Theexpressioninanyofthethreebasiccubiclatticesis
thesame,whereaisthelatticeparameter.

q
Thespinwavedispersion
relationforachainofatoms.
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93

ExcitationofspinwavesisresponsibleforthefallofmagnetizationwithincreasingTwhichismuch
faster than expected from molecularfield theory, given J. They also contribute to resistivity and
specificheat,givingaT3/2variationofspecificheatatlowtemperature.

Spontaneousmagnetizationofaferromagnet,comparedwithmeanfieldtheory.

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Magneticneutronscattering
Elastic (Bragg) scattering The neutron possesses a small magnetic moment. In addition to nuclear
scattering by the nuclear potential, it is also scattered by the unpaired electron spins in a solid. Extra
Bragg peaks of magnetic origin may appear, from which the magnetic structure can be inferred. If the
inetron,withincidentwavevctorKisscatteredintoastateK,theBraggconditionisthatthescattering
vector=KKshouldbeareciprocallatticevectorGhkl.
Forexample,magneticBraggscatteringcanbeusedtodetectantiferromagneticorder

Neutronscatteringfromironandchromium,showingthemagneticpeaks

Inelasticscattering:Inelasticneutronscattering,wheretheincidentneutronloses(gains)energyby
excitinganelementaryexcitationofenergyE=hqandwavevectorq,canbeusedtomapspinwave
dispersionrelations.ForFe,Dsw=8Jm2.(500meV2).Theenergyinamodeoffrequencyqcontaining
nqmagnonsis(nq+1/2)q
Illustrationofelastic|K|=|K|andinelasticscatteringprocesses.K=K+q+Ghkl.
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Data on some antiferromagnets.

Material

TN(K)

Mn

96

-200

CoO

291

-330

NiO

525

-1300

MnF2

85

-113

950

-2000

Fe2O3
Data on some ferrimagnets.

Material

TC(K)

m0 (B/formula)

0M at 290 K (T)

Fe3O4

840

4.0

0.63

Fe2O3

1020

3.3

0.54

Y3Fe5O12

560

5.0

0.18

BaFe12O19

742

20.0

0.48

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8Magneticapplications
Magnets play a pivotal role in our civilization. Soft magnets are used to generate electricity, and convert electrical
energy into mechanical energy in motors and actuators. Hard magnets generate magnetic fields with no continuous
expenditure of energy. Magnets are used to exert forces in static applications and in permanent magnet machines.
Semihard material is used as the erasable recording medium on tapes and hard disc discs. Data is written using
micronscale electromagnets and read using tiny spinvalve sensors which respond to the stray field a few tens of
nanometersabovethesurfaceofthedisc.

8.1Hardmagnets
Permanentmagnetsareferromagnetswithawidehysteresisloop.Oncemagnetized,theysitataworking
point in the second quadrant of the loop which is determine by the magnet shape and the rest of the
magneticcircuit..
Permanentmagnetsgeneratemagneticfluxwithnocontinualexpenditureofenergy!
TheBfieldmaybeuniformornonuniform,staticortimedependent.ThemagneticfluxdensityB0inthe
airgap is the natural field to consider in permanent magnet applications because flux is conserved in a
magneticcircuit,andforcesonelectricchargesandmagneticmomentsalldependonB.
The best permanent magnets are intermetallic compounds of a ferromagnetic 3d element and a 4f
element; e.g. SmCo5 or Nd2Fe14B. Most common are the cheap hexagonal ferrites BaFe12O19 and
SrFe12O19.Thesepowdersaresometimesbondedinplastic
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Applicationsdependononeofthefollowingeffects:
Astaticuniformfieldgeneratestorqueonamagnetandtendstoalignpreexistingmagneticmoments
since=mB.Thecompassisanexample.
ChargedparticlesmovingthroughauniformfieldwithvelocityvaredeflectedbytheLorentzforceF=
qvB,whichcausesthemtomoveinahelix.(c.fBuschse/mexperiment)
If the charged particles are electrons confined in a conductor of length L where they constitute a
current I flowing perpendicular to the field, and the Lorentz force leads to the familiar expression F =
BIL.Thisisthebasisofelectricmotorsandotherdrives.
Conversely, moving a conductor through the uniform field generates an induced electromotive force
(emf) given by Faraday's law = d/dt where (=BA) is the flux threading the circuit of which the
conductorformsapart.Eddycurrentsaregeneratedtoopposethemotion.
Spatially nonuniform fields offer another series of useful effects. They exert a force on a magnetic
momentgivenbytheenergygradientF=(m.B).
They also exert nonuniform forces on moving charged particles, which can be used to focus ion or
electronbeamsorgenerateelectromagneticradiationfromacceleratingelectronbeamspassingthrough
thenonuniformfield.
Timevaryingfieldscanbeproducedbydisplacingorrotatingthemagnets.Thismayinduceanemfin
aconductoraccordingtoFaraday'slawexertforcesontheinducededdycurrents.Uniformtimevarying
fieldsarevaluableformagneticmeasurements.
Finally, a spatially nonuniform timevarying field will exert a timedependent force on a magnetic
moment or particle beam. Applications include magnetic switches and magnetic measurements such as
theFaradaybalance.
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Examplesofpermanentmagnetapplications.

_________________________________________________________
Field

Magneticeffect

Application

Uniform

Zeemansplitting
Torque
Halleffect,
Magnetoresistance
Forceonconductor
Inducedemf

magneticresonanceimaging
magneticpowderalignment
sensors

Forcesoncharged
particles
Forceonparamagnet
Forceoniron
Forceonmagnet

beamcontrol,radiationsources
(microwave,uv,Xray)
mineralseparation
holdingmagnets
bearings,couplings,maglev

_________________________________________________________

Nonuniform

TimevaryingVariablefield
Forceoniron
Eddycurrents

motors,actuators,loudspeakers
generators,microphones

magnetometery
switchableclamps
brakes,metalseparation

Theworkingpointofapermanent
magnetinthesecondquadrantof
thehysteresisloop.

_________________________________________________________
Other uses of magnets,in acupuncture, pain control, electrochemistry, supression of wax formation in
oilwellsorcontroloflimescaledepositsinpipescarryinghardwateraredifficulttoclassify,butworthy
ofinvestigation!
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Holdingmagnets
Magnetsexertforcesoneachother,andonotherferromagneticmaterialssuchassoftiron.Theplastic
bondedferritemagnetsonthefridgearemagnetizedinapatternofstripesabout3mmwidemagnetized
alternatelyinwardsandoutwardsfromthesheet.
Checkthisbygentlydraggingtwopiecesof
plasticmagnetpasteachother!

- -

Magnetizationpattternofplasticmgnetsheet.

Toworkoutthemaximumforcethatcanbegeneratedatthefaceofamagnet,consideratoroidthatis
cutintotwoCshapedsegmentsandthenseparatedslightly.
IftheseparationisdandthecrosssectionareaisAg,the
energyappearingintheairgapsis2(1/2)oHg2Agd
=Bg2Agd/o.Theworkdoneseparatingthesegment
Bg
is2Fd,hencetheforceperunitareais
F/Ag=Bg2/2o
Forcesofupto40Ncm2canbeachievedforBg=1T.

Amagnetictoroidcutandseparatedtoproducea
fieldintheairgap.

Thefluxdensityatthesurfaceoftheplasticmagnetisabout50mT.Estimatetheforceonapiecethe
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100

Nonuniform magnetic fields offer social benefits from the tiphead to the haematology laboratory. The
expressionfortheenergyofapreexistingmagneticmomentminafieldHisom.H,leadingto
F=o(m.H)
.

However when a small moment m =Vis induced by the field in a material of volume V and
susceptibility,theexpressionbecomes
F=(1/2)oV(H2)

Thisexpressionisthebasisofmagneticseparation

Magnetic separation a) open gradient

separation;b)electromagneticseparation
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Generationofmagneticfields
Uniform fields. The magnetic field produced by a point dipole of moment m Am2 is quite
inhomogeneousInpolarcoordinates,itis
Hr=2mcos/4r3,

H=msin/4r3,

H=0

The field due to an extended line dipole of length L and dipole moment Am per unit length is
significantlydifferent:
Hr=cos,/4r2,
H=sin/4r2,
H=0
The magnitude of H,(Hr 2 +H+His now independent of and its direction makes an angle 2
withtheorientationofthemagnet.

Comparisonofthemagneticfieldproducedbya)apointdipolemandb)alinedipole.
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Magneticcircuitsmadeoflongcylindricalsegmentsmaybeusedtogenerateuniformfields.Anopen
cylinderoradesignwithflatcuboidmagnetsandasoftironreturnpathisusedtofornuclearmagnetic
resonance(NMR).Permanentmagnetfluxsourcessupplyfieldsoforder0.3Twithhomogeneityof1
partin105inawholebodyscanners.

Designsformagneticcylinderswhichproduceauniformtransversefield.

Figure(c)showsadesignwherethedirectionofmagnetizationofanysegmentatangularposition in
thecylinderisat2fromtheverticalaxis.Accordingtotheequationsforthelinedipole,allsegments
nowcontributetocreateauniformfieldacrosstheairgapinaverticaldirection.Unlikethestructureof
Fig (a), the radii r1 and r2 can take any values without creating a stray field outside the cylinder. This
ingeneousdeviceisknownasaHalbachcylinder,Thefieldintheairgapis
B0=Brln(r2/r1)
Inpracticeitisconvenienttoassemblethedevicefromntrapezoidalsegments,asillustratedinfig.(d)
forn=8.
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ThereisnolimitinprincipletothemagnitudeofthefieldthatcanbeproducedinaHalbachcylinder,but
inpracticethecoercivityandanisotropyfieldofthemagnetslimittheultimateperformance.Becauseof
thelogarithmicdependencein(8.5)andthehighcostofrareearthmagnets,itbecomesuneconomicto
usepermanentmagnetstogeneratemagneticfieldsthatexceedtwicethetheremanence.
VariablefieldsTwoHalbachcylinderswiththesameradiusratio =r1/r2canbenestedinsideeach
other.Rotatingthemboththroughanangleabouttheircommonaxisgeneratesavariablefield2Br
lncos.Permanentmagnetvariablefluxsourcesarecompactandparticularlyconvenienttousesince
theyhavenoneofthehighpowerandcoolingrequirementsofacomparableelectromagnet.
AcommercialMULTIMAGsystemmadeby
MagneticSolutionsLtdusesanestedHalbach
magnetmadeof12kgNdFeBmagnetto
generate1.8Tina25mmbore.These
devicesareidealforcompactinstrumentation
suchasbenchtopvibratingsamplemagneto
meteroramagnetoresistancemeasurment.
Permanentmagnetvariablefluxsourcesare
expectedtograduallydisplaceresistive
electromagnetstogeneratefieldsofuptoabout
2T,buttheycannotcompetewith
superconductingsolenoidsinthehigherfield
range.Theconventionallaboratoryelectromagnet
isadinosaur.

Permanentmagnetvariablefluxsourcebasedona
rotatabledoubleHalbachcylinder.
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A MULTIMAG permanentmagnet variable flux source and controller. The magnet head of the type shown in the
previousfigureproducesavariablefieldofupto1.8Tinanytransversedirectioninthebore
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Permanentmagnetmotors
Motors whose operation depends on permanent magnets are produced in quantities > 10 8 units/year.
Small dc permanent magnet motors are found in domestic appliances and consumer electronics. Dc
servomotorsarefoundinmachinetools,robotsandotherindustrialmachinery.Permanentmagnetscan
alsobeusedtoadvantageinlargeindustrialdrivesandelectricvehicles
Thetwomainpartsofarotarymachinearethefixedstatorandtherevolvingrotor.
DC motor designs include both permanent magnets and electromagnet current windings. A permanent
magnetonthestatorwillcreatesafieldatthecurrentcarryingwindingsoftherotor.Amechanicalor
electroniccommutatorwithbrushesdistributescurrenttothewindingsinsuchawaythatthetorque
ontherotorisalwaysinthesamesense.
Conversely,thedevicewillfunctionasagenerator,producinganemfUinthewindingsifitisdrivenat
anangularvelocity.
Thetorquecharacteristicofthedcmotoris().Iftheradiusoftherotorwindingisr,thefluxdensity
ofthemagnetisBandtherearenconductorsoflengthLperpendiculartoB,eachcarryingacurrentI,
then=nrBIL.TheoutputpowerwillbeequaltoUI,wherethebackemfUgeneratedastherotor
turnsis2rBLperconductor.Thenumberofconductorsconnectedinseriesisn/2,soU=nrBL.Ifthe
applied voltage is V = U + RI,where R is the resistance of the windings, the torque equation for the
motoris
=K(VK)/R
whereK=nrBListhetorqueconstantofthemotor.Torqueisgreatestatstartup,when andis
proportionaltothefluxdensityproducedbythemagnet.ItfallstozerowhenV=K.
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8.2Softmagnets

DCmotordesigns:(a)brushmotorwith
magnets on the stator and (b) brushless
motorwithmagnetsontherotor.

Asoftmagneticmaterialshouldhaveminimalhysteresisandhighpermeability.Insomerangeoffield,
theB(H)characteristicislinear
B=H orB=0rH
where the relative permeability r is a pure number. The permeability is smaller near the origin of the
hysteresisloop,wherer=itheinitialpermeability,thanitisforslightlylargerfieldswhereitreachesa
maximumvaluemax.
Valuesofmaxcanexceed106inthesoftestmaterials.HenceBisgreatlyenhancedcomparedtothefree
space value 0H. The permeability and loop shape can be modified by annealing, especially in a weak
magneticfield.
TherelationbetweenrelativepermeabilityandsusceptibilityfollowsfromB=0(H+M);dividingby
H,itfollowsthatr=1+r.
Softmaterialsareusedforstaticandacapplications.Staticandlowfrequencyapplicationsaresuchas
fluxguidanceandconcentrationinmagneticcircuits.Majoracapplicationsincludecoresfor
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transformersandinductors.

Hysteresisinasoftmagneticmaterial.B(H)and
0M(H)areindistinguishableinsmallfields.
Softmagneticmaterialsandapplications.
static
lowfrequency
audio
frequency

Frequencyrange
<1Hz
1Kz1kHz
100Hz100kHz

radiofrequency 0.11000MHz
microwave
>1GHz

materials
Softiron,FeCo(permendur)
isotropic or grain oriented
FeSi
permalloy foils, magnetic
glasses, sendust powder, Mn
Znferrite
MnZnferrite,NiZnferrite
YIG,Liferrite

applications
electromagnets,relays
transformers,
motors
generators
inductors, transformers for
switchedmode power sup
plies,tvflybacktransformers
inductors,antennarods
microwave
isolators,
circulators,phaseshifters

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Magneticcircuits
Transformers, motors and generators include soft iron cores to generate and guide flux. Eddycurrent
losesarereducedbyusingthinlaminationsofmaterialwithahighresistivity.Transformerefficiencies
are>99%.
Eddycurrent losses at high frequencies (> 100 kHz) are eliminated by using insulating ferrimagnetic
oxides,theferrites,toguideandconcentratetheflux.
Electromagnetsconsistoffieldcoilstogeneratethefield,anironyoketoguidethefluxandpolepieces
toconcentratethefluxintheairgap.Fluxguidanceandconcentrationinelectromagnetsrequiresmaterial
with thehighest polarization and very little remanence. Usually pure soft iron or Fe 65Co35 is used. For
bestresults,taperedpolepieceswithanangleof55areused.

An electromagnet

Electromagnetic relays and solenoid valves are miniature electromagnets where an iron core is
magnetizedandexertsaforceonanotherironmember.TheforceperunitareaifthegapfluxisB gis
Bg2/20

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Magneticshielding
Shieldingofweakdcorlowfrequencyacfields(e.g.theEarthsfield)requiresmaterialtoprovidean
easyfluxpatharoundtheshieldedvolume.TheshieldingratioRistheratioofthefieldoutsidetothe
field inside. Values of R 100 are achieved in low fields. The shielding material is chosen so that its
polarizationisunsaturatedbythecollectedflux.dcshieldsareoftenmadeofpermalloyNi80Fe20,which
hasnoanisotropyormagnetostriction,andisthereforeimmunetoshockandstrain.

Magneticshielding.

8.3Magneticrecording

Digitalandanalogrecordingisahugeindustry,consuminglargequantitiesofferriteandothersemihard
magneticmaterialsforrecordingmedia,andusingsophisticatedminiaturemagneticcircuitsintheread
andwriteheads.
The magnetic record is generally in the plane of the medium. Only magnetooptic recording uses
perpendicularlymagnetizedmedia.
Thedataarerecordedontracksonthemediawhosewidthisdeterminedbythewidthofthewritehead.
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Schematicofinplaneandperpendicularmagneticrecording.

Digitaldataarerecordedasasequenceofshortbitswithsaturationremanenceparallelorantiparallelto
thetrack.
Data densities on hard discs have been increasing by 60%/year. The current state of the art in the
laboratoryis80bits/m2(52Gbits/squareinch).10bits/m2willshortlyenterproduction
Analoguerecordinginvolvesasignalofcontinuouslyvaryingamplitudeandfrequency,whichmustbe
mappedlinearlyontotheremanentmagnetizationofthemediumforhighfidelity.Butremanenceisnot
linear in applied field. To achieve a linear response an ac bias at 100kHz is applied to saturate the
magnetization.Theanhystereticremanenceisthenproportionaltothesignal.
Magneticmediaaremadeofsemihardmagneticmaterialswithsufficienthysteresistoprovidea
permanentrecordofthedata,butsoftenoughtobereadilyremagnetizedinthefieldproducedbythe
writehead.Themediaconsistofthinfilmsordispersionsofsingledomainparticlesinapolymermatrix,
withaneasydirectionofmagnetizationparalleltothesubstrate.Commonlyusedmaterialsforparticulate
mediaontapesandfloppydisksareacicular(needlelike)Fe2O3(especiallywithCosurfacedoping),
CrO2andironmetalpowders.Coercivityisabout50kAm1.
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AnFepowderusedformagneticrecordingtapes.

ThethinfilmmediaonharddiscsaregenerallyhcpCoCralloys,withacoercivityofabout160kAm1.
Asrecordingdensitiesincrease,thereisatrendtomaterialswitheverhighercoercivities,H c>200kAm
1
,sothatpermanentmagnetmaterialslikeBaFe12O19mightbeconsideredasrecordingmediainfuture.
Theyarealreadyusedforcertainmagneticrecordslikethoseoncreditcardsoridentitycardswhichare
notintendedtobeerased!
ThedigitalinformationisencodedinthedirectionofmagnetizationofagroupofNsingledomaingrains
inathinfilm,locatedatanidentifiablepointsonatrack.Asquarehysteresisloopisdesirableandfora
goodsignal/noiseratio,theindividualgrainsshouldbemagneticallydecoupled.
The smallest grain size is determined by the condition that superparamagnetic fluctuations of the total
magnetizationmustnotbeexcitedthermally.Thehighestrecordeddensitieswillthereforebefoundfor
magneticmediamadefromtinyparticlesofmaterialswiththehighestpossibleanisotropy.Inthecaseof
BaFe12O19,K1is0.33MJ/m3andtheconditionforsuperparamagneticblockingatroomtemperatureofa
particleofvolumeV,K1V/kBT>40,impliesaparticlesizeofafewnanometers.Ifthefilmthicknessis
10nmandNcanbereducedto100,thenthebitsizewillbe5,000nm 2,leadingtoultimatedensitiesof
order200bits/m2[130Gbits/inch2].
Higher densities will demand patterned media where singledomain particles in determined positions
alongatrackareindividuallyaddressed
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Thewritehead

Athinfilmwritehead.

Thethinfilmwriteheadfordatarecordingonharddiscsconsistsofaflatcoilsandwichedbetweentwo
films of a soft material such as permalloy or Fe94Ta3N3 which form the poles of a miniature
electromagnet.Thewrittenbitsarenarrowbandsorientedacrossthetrack,whicharemagnetizedbythe
strayfieldattheedgesofthetwoflatpoles.Thegapisabout200nm.
Ultrahighdensityrecordingwillrequirematerialwithapolarization>2T.
Thereadhead(anisotropicmagnetoresistanceandspinvalves)
Thedirectionofmagnetizationofthemediummaybesensedviathestrayfieldmeasuredclosetothe
surfaceusinganinductivereadheadorathinfilmmagnetoresistancesensor.
A the simplest magnetic twoterminal device for use as the read head is an anisotropic
magneroresistance (AMR) sensor. The resistance of 3d metals and alloys such as permalloy depends
slightlyontheanglebetweenthecurrentandmagnetizationdirections.TheresistanceisR0+Rcos2,
andthemagnitudeoftheeffectR/Rcanreachabout2%.
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ThethinfilmAMRsensorhasalinearresponsewhen 45.Abiasfieldgreaterthanthefieldtobe
sensed canbeprovidedbyanadjacent permanentmagnetlayer.The biasfieldeliminatesdomainsand
leadstoasingledomainsensorwithnoBarkhausennoise.

AnAMRreadhead

Thespinvalveisanothermagnetoresistivedeviceusedinreadheadsforthehighestdensityrecording.It
is composed of a sandwich or multilayer of alternate magnetic and nonmagnetic metallic layers. The
couplingbetweenthetwoferromagneticlayersM1andM2isweak,andoneofthelayersisusuallypinned
byexchangecouplingtoanantiferromagneticlayersuchasNiO(exchangebias).Thefreelayercanthen
flipinasmallexternalfield.Theresistanceofthedevicechangsby20%ormoreaccordingtowhether
theconfigurationofthetwolayersisor.
Thegiantmagnetoresistiveeffectonmagneticmultilayerswasdiscoveredin1989byFertandcoworkers
inParis.Inlessthat10yearsitbecamethebasisofnewcomputertechnology,thankstothedevelopment
workofParkinandcoworkersatIBM
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Aspinvalvereadhead

Highdensitymagneticrecordingisthelatestin
aseriesofspectaculardevelopmentsinmagnetic
technology.

ImprovementsofthearealdensityofIBMharddiscs.1bit/m2
correspondsto0.645Gbitssquareinch.

Thenextdevelopmentonthehorizonismagneticrandomaccessmemory(MRAM).Structureslikethe
spin valve are densely integrated onto chips with associated electronics to provide a new type of
nonvolatilememory,whichmaywithinthenext10yearsentirelyreplacesemiconductormemoryaswell
astheharddisk!
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