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SommerfeldsFreeElectronTheoryofMetals|PhysicsAssignment

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SommerfeldsFreeElectronTheoryofMetals
HomeSommerfeldsFreeElectronTheoryofMetals
In1928,byapplyingquantummechanicalprinciples,ArnoldSommerfeldsucceededinovercomingmany
ofdrawbacksoftheclassicalfreeelectrontheory,whileretainingalltheessentialfeaturesoftheclassical
freeelectrontheory.Hisapproachisbaseduponquantizationofelectricalenergylevels.Herealisedthe
roleplayedbyPauliexclusionprincipleinrestrictingtheenergyvaluesofelectron.Thetheoryproposed
knownasQuantumFreeElectronTheory
Themainassumptionsofquantumfreeelectrontheoryare,
1.Theenergylevelsoftheconductionelectronsarequantised.
2.ThedistributionofelectronsinvariousallowedenergylevelsoccurasperPauliexclusion
principle.
3.However,thefollowingassumptionsofclassicalelectrontheorycontinuetobeapplicablein
quantumfreeelectrontheoryalso.
4.Theelectronstravelinaconstantpotentialinsidethemetalbutstayconfinedwithinitsboundaries.
5.Boththeattractionbetweentheelectronsandthelatticeions,andtherepulsionbetweenthe
electronsthemselvesareignored.
FermiEnergy
Duetothequantizationrules,amaterialinsolidstatepossessasetofallowedenergylevels.Forametal
containingNfreeelectrons,therewillbeNsuchallowedenergylevels,whichareseparatedbyenergy
differencesthatarecharacteristicofthematerial.Theallowedenergyvaluesfortheconductionelectrons
inthemetalarealsoquantised,arerelatedtotheenergylevelsofthemetal.AsperthePauli
exclusionprinciple,eachenergylevelcanaccommodateamaximumoftwoelectrons,onewithspinup
andtheotheronewithspindown(Figure11.1).

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FIGURE11.1FermiEnergy
Theallowedenergyvaluesoftheelectronarerealisedintermsofoccupationoftheallowedenergy
levels,undercertainrules.Whenthefillinguptheenergylevelsisundertakentheuniversalrulesthatany
systemwhichisfreetendstogostateoflowestenergycomesintopicture.
Thusapairofelectrons,onewithspinup,andotherwithspindownoccupythelowerslevel.Thenext
pairofelectronsoccupythenexthigherlevel,andsoon,tillalltheelectronsinmetalareaccommodated.
However,therewillbemanymoreallowedenergylevelsavailableforoccupationbytheelectrons.The
energyofthehighestoccupiedlevelatzerodegreeabsoluteiscalledFermienergy,andtheenergy
levelisreferredtoastheFermilevel.TheFermienergyisdenotedasEF.
Whenthereisnoexternalenergysupplyfortheelectrons,suchasthermalenergyorelectricalenergy,the
electronsarefree,andthussettleinthelowestallowedenergystateavailable.Thusatatemperatureof
absolutezero,andwhenthemetalisnotintheinfluenceofanyexternalfield,alltheenergylevelslying
abovetheFermilevelareempty,andthoselyingbelowarecompletelyfilled.Sincetherearetwo
electronsineachenergylevel,outoftheNallowedenergylevelsN/2ofthemwillbeoccupied.
Fermilevel
TheFermilevelisanenergylevelmidwaybetweentopsurfaceofvalencebandandbottomsurfaceof
conductionbandasshowninFigure11.2.

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IfEVistheenergycorrespondingtotopsurfacevalenceband,ECistheenergycorrespondingtobottom
surfaceofconductionbandandEFistheFermienergycorrespondingtoFermilevel,then

FermiFactor
Whenthetemperatureisnotatabsolutezero,thematerialwillbereceivingthermalenergyfrom
surroundings.Atordinarytemperature,theamountofenergywillbequitesmall,becauseofwhichthe
electronsoccupyingenergylevelsbelowtheFermilevelcannotabsorbthethermalenergy.Itisbecause,
thereisnoavailabilityofunoccupiedhigherenergylevelsintowhichtheelectroncancomeinto,dueto
theincreaseinenergybytheabsorptionofthermalenergy.However,thereareunoccupiedhigherenergy
levelswhichareabovetheoccupiedenergylevelsatsmallenergydifferences.Theyarelocatednear
Fermilevel.Thosearetheenergylevelsintowhich,theelectronsintheenergylevelsnearFermilevel,
arecapableofbeingexcited**.
Duringthermalexcitation(i.e.,T>0),theelectronswhichabsorbthethermalenergymoveintohigher
energylevelswhichwereunoccupiedatzerodegreeabsolute(i.e.,T=0).Thoughsuchexcitationsseem
toberandom,theoccupationofvariousenergylevelobeyastatisticaldistribution***calledFermiDirac
distribution,oncethesystemisinthermalequilibrium(i.e.,atasteadytemperaturestate).
Theprobabilityf(E)thatagivenenergystatewithenergyEisoccupiedatasteadytemperatureT,is
givenby
*ThequantityofthermalenergyisgivenbykbT,wherekBisBoltzmannconstant.Aroomtemperature
kBT=0.0025eV.ComparethiswithFermienergywhichisoftheorderof5eV.
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**Sincesuchelectronsconstituteonlyasmallfractionofthetotalnumberofelectronsinthemetalasa
whole,thespecificheatofthematerialbecomeslow.Thus,reasonforfailureofclassicalfreeelectron
theorytoaccountforlowspecificheatofmetalsisnowunderstood.
***Thestatisticaldistributiondealswiththequestionastowhatistheprobabilityoccupationofa
particularenergylevel.

f(E)iscalledtheFermifactorandisdefinedasfollows:
Fermifactoristhedistributionfunctionwhichgivestheprobabilityofoccupationofagivenenergystate
formaterialinthermalequilibriumintermsoftheFermienergy,Boltzmannconstantandthe
temperature.
ThedependenceofFermifactorontemperature,andtheeffectonoccupancyofenergylevelisshownin
Figure11.3.

Letusconsiderthedifferentcasesofdistribution
(i)ProbabilityofoccupationforE<EFatT=0
WhenT=0andE<EF

AtT=0K,alltheenergylevelsbelowtheFermilevelareoccupied.
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(ii)ProbabilityofoccupationforE>EFatT=0K
WhenT=0,andE>EF

Further,forE>EF,theprobabilityvaluefallsofftozerorapidly(Figure11.3).Theabovediscussionon
thevariationf(E)withE,bringsforththepointthat.
TheFermienergyisthemostprobable,ortheaverageenergyoftheelectronacrosswhichtheenergy
transitionsoccursattemperatureabovezerodegreeabsolute,whichresultintheconductivityofthe
metal.ThismaybeconsideredasthephysicalbasisfortheconceptofFermienergy.
CalculationofFermiEnergyatT=0K
LetthevalueofEFof0KbedenotedasEF0.Also,ifwedenotethenumberofelectronsperunit
volume,whichpossessenergyonlyintherangeEand(E+dE),byN(E)dE,then,N(E)dEisgivenby
theproduct
densityofavailablestatesintheenergyrangeEandE+dEprobabilityofoccupationofthoseenergy
levelsbytheelectron.
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But,probabilityofoccupationofanygivenenergystatebytheelectronisgivenbytheFermifactorf(E).
N(E)dE=g(E)dEf(E)
Thenumberofelectronsperunitvolumeofthematerialncanbeevaluatedbyintegratingtheabove
expressionfromE=0toE=Emax,whereEmaxisthemaximumenergypossessedbytheelectrons

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FermienergyatT>0K
TheFermienergyEF,atanytemperatureTingeneralcanbeexpressedintermsofthroughtherelation

(FermiTemperature(TF)
Fermitemperature(TF)isthetemperatureatwhichtheaveragethermalenergyofthefreeelectronina
solidbecomesequaltotheFermienergyat0K.Butthethermalenergypossessedbyelectronsisgivenby
theproductkBT.

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whichisquiteanexaggeratedtemperaturetoberealizedinpractice.
FermiVelocity(VF)
Theenergyoftheelectron,whichareattheFermilevelisEF.Thevelocityoftheelectronswhichoccupy
theFermileveliscalledtheFermiVelocityvF.

ComparisonClassicalFreeElectronTheoryandQuantumFreeElectronTheory
Similaritiesbetweenthetwotheories
Thefollowingassumptionsapplytoboththetheories:
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1.Thevalenceelectronsaretreatedasthoughtheyconstituteanidealgas.
2.Thevalenceelectronscanmovefreelythroughoutthebodyofthesolid.
3.Themutualrepulsionbetweentheelectrons,andtheforceofattractionbetweentheelectronsand
ionsareconsideredinsignificant.
Differencebetweenthetwotheories
ClassicalFreeElectronTheory

QuantumFreeElectronTheory

1.Thefreeelectrons,whichconstitutethe
electrongascanhavecontinuousenergy
values.

1.Theenergyvaluesofthefreeelectronsare
discontinuousbecauseofwhichtheenergy
levelsarediscrete.

1.Itispossiblethatmanyelectronmay
possesssameenergy.

1.ThefreeelectronsobeythePauliexclusion
principle.Hencenotwoelectronscan
possesssameenergy.

1.Thepatternofdistributionofenergy
amongthefreeelectronobeyMaxwell
Boltzmannstatistics.

1.Thedistributionofenergyamongthefree
electronsisaccordingtoFermiDirac
statisticswhichimposesasevere
restrictiononthepossiblewayinwhichthe
electronsabsorbenergyfromanexternal
source.

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