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Sinceyourfreshmenyear,youhavebeenusingelectronconfigurationnotation.Itisan
easyandintuitivewaytowriteelectronicstates,andcanevenbeusedtoexpressexcited
states.Forexample,thegroundstateofCis1s22s2p2Wecouldwriteanexcitedstateas
1s22s2p13s1
Whatswrongwiththis?
Thisnotationisnotspecificenough.1s22s2p2isNOTasinglestate.Thereare36different
microstatesthathavethissameconfiguration.Hereareafewofthem:
Noticethattheyhavedifferentmultiplicitiesandangularmomenta.Theenergiesofthese
statesareNOTthesame.Unlesswewanttowriteoutallofthemicrostateseverytimewetalk
aboutelectronicstates,weneedtoinventacompactnotationthatcansumupallofthis
informationinaconciseandusefulway.
Theprincipalquantumnumbern
nisameasureofthequantizedenergyoftheelectron.Ittellsyouwhichenergylevel
theelectronoccupies.Thelowestpossiblevalueisone,andthereisnotheoreticallimittohow
highitcango(althoughinpractice,reachingveryhighlevelsofncausesionization,atwhich
pointitstopsmakingsensetotalkaboutenergylevels).Theprincipalnumbercanbeusedto
calculatethequantizedenergybythis(hopefullyfamiliar)formula:
En=RhcZ2/n2
whereRistheRydbergconstantandZistheatomicnumber
Theorbitalangularmomentumquantumnumberl(littleel)
listhequantumnumberthatdeterminesthemagnitudeoftheelectronsangular
momentum.ldoesnotsayanythingaboutthedirectionoftheangularmomentum.The
formulais:
L2=2l(l+1)whereL2isthemagnitudeoftheangularmomentum
Electronsinhigherenergylevels(e.g.highernnumbers)haveawiderrangeoflvaluesto
choosefrom.Lcanbeanyintegernumberbetweenn1and0.Forexample,anelectronin
n=4couldhaveanlvalueof3,2,1or0.Butthereisabetterwaytothinkaboutl.
Theangularmomentumq#tellsyouwhichtypeoforbitaltheelectronisin.Itfollowsa
verysimplecode:
l=0sorbital
l=1porbital
l=2dorbital
l=3forbital
Youshouldknowfromgeneralchemistrythatthefirstenergylevelonlyhasansorbital,that
thesecondenergylevelhassandporbitals,andsoon.Soyoudontreallyneedaformulato
figureoutwhichcombinationsoflandnarepossible.Youshouldrealizerightawaythat
n=1l=2isimpossible,becausetherearentdorbitalsonthefirstenergylevel!
Notethattheserulesimplythatdifferenttypesoforbitalsgrantdifferentamountsof
angularmomentumtoanyelectronsthatoccupythem.sorbitalsareextremelysymmetric,so
theyhavealowvalueofL2[20(0+1)=2].forbitalsareflatterandmoreplanar,sotheyhave
higheramountsofangularmomentum[23(3+1)=92]
Themagneticquantumnumberml
mltellsyouwhichdirectiontheelectronsangularmomentumispointing.Itcanbe
usedtocalculatehowmuchofthemomentumisprojectingontothezaxisoftheatom:
Lz=mlwhereLzisthezcomponentoftheangular
momentum
mltellsyouwhichsuborbitaltheelectronisin.Itcanrangeinvaluefromltol.Again,
youshouldntneedaformulatorealizewhatcombinationsmakesense.Youshouldknowthat
thereisonlyonesorbitalperlevel,threeporbitals,fivedorbitals,andsoon.
___
ml0
Forl=0(stype),mlmustbe0
_________
_______________
101 21012
Forl=1(ptype),mlcanbe1,0,1Forl=2(dtype),mlcanbe2,1,0,1,2
Interlude:inherentspin
Allparticleshaveapropertycalledspin.Spinistheinherentangularmomentumofa
particle.Weoftenpretendthatspinistheangularmomentumthatcomesfromtheparticle
rotatingaboutitsownaxis.Formanypurposes,thisisaverygoodapproximationtothetruth.
Forexample,anelectronsspincausesittoprojectamagneticfield,whichiswhatyouwould
expectfromarotatingchargedbody
However,themagneticdipoleproducesthiswaydoesnotexactlymatchwithwhatclassical
physicswouldpredict.
Thereareotherimportantdiffencesbetweenthequantummechanicalconceptofspin
andtheclassicalconceptofrotation.Mostsignificantly,spinisafixedvalue.Allelectrons
everywherehavetheexactsamespin.Itcannotbemadetospinfasterorspinslower.Itis
afixedphysicalproperty,likemassorcharge.
Allparticleshaveaspinquantumnumber,calleds,thatcanbeusedtocalculatethe
inherentangularmomentum.Theformulais:
S2=
Electronsallhaveansvalueof,sotheinherentangularmomentumofanelectronis:
S2=
Thisnumberwillbethesameforallelectronseverywhere.Pleasenotethatthe
inherentangularmomentumisdifferentfromthenormalangularmomentumthatwewere
discussingearlier.Thefirstonecomesfromtheelectronsspin,andthesecondonecomes
fromtheelectronsmotionabouttheorbital.
Thespinmagneticquantumnumberms
Allelectronshavethesameamountofinherentangularmomentum,butangular
momentumisavectorquantityandcanpointindifferentdirections.Justlikehowmltoldyou
whichdirectiontheelectronsorbitalangularmomentumwaspointingin,mstellsyouwhich
waytheelectronsinherentangularmomentumpoints.
Wheninanorbital,electronspinscanonlybeorientedintwodirections,whichwe
commonlycallupanddown.Therearenoinbetweenstatesallowed.Whentheelectronis
orientedalongthepositivezaxis,msisequalto.Whenthespinispointedalongthenegative
zaxis,msisequalto.
Thewordsupanddownaremisleading.Theelectronspinsarenotpointingdirectly
alongthezaxis.Moreover,anupelectronisnotnecessarilypointingpegoppositetoa
downelectron.Howisthispossible?Itisbecausethespinaxisisatanangle:
Whenwesaythatanelectronisorientedup,whatwemeanisthatthezcomponentofits
inherentspinispointingup,notthatthewholevectorisliterallypointingstraightupthezaxis.
Thespinmagneticquantumnumbercanbeusedtocalculateexactlyhowmuchofthe
electronsinherentangularmomentumisorientedalongthezaxisbythissimpleformula:
Sz=ms
Sincetheonlypossiblevaluesformsareand,Szwillalwaysbeequaltoeither
or
Theillustrationaboveisabetterwaythinkingofelectronorientationthanthesimpleup
anddownmodel,butitisstillmisleading.Thediagramshowstheelectroninadefinite
orientation,butelectronsarequantummechanicalobjectsandaresubjecttoquantum
uncertainty.Wewillreturntothisissuewhenwestarttalkingaboutmultiplicity.
Symbol
Name
Principal
quantum
number
orbital
angular
momentum
magnetic
quantum
ml
ms
Allowed
Range
[1,]
Associated
property
energy
[n,0]
Angular
momentum
(scalar)
Angular
momentum
(zcomponent)
Spin
momentum
(zcomponent)
Spin(scalar)
[I,l]
spinmagnetic or1/2
quantum
number
Inherentspin 1/2
number
Formula
Notes
En=RhcZ2/n2 Indicates
energylevel
L2=2l(l+1) Indicates
typeof
orbital
Lz=ml
Indicatessub
orbital
Sz=ms
S2=
Indicatesspin
direction
s=1/2forall
electrons,no
matterwhat
AtomicTermSymbols
Convenientlyforchemists,anatomselectronicstatedependsentirelyonitsunfilledsubshells.
Becauseelectronsdistributethemselvesinasymmetricmanner,theinnershellelectronsend
upcancelingouteachothersmomenta.Foranatomintheconfiguration1s22s2p2,onlythe
twopelectronsmatter.Foranatomintheconfiguration1s22s12p1,wehavetoexaminethe
2sand2pelectrons.
Atomshavequantumnumbersthataredirectlyanalogoustotheelectronicquantumnumbers.
ThetotalorbitalangularmomentumquantumnumberL
Onemightnaivelythinkthatyoucouldgetthetotalangularmomentumofanatombysimply
addingupthelvaluesoftheindividualelectrons.Theproblemwiththisideaisthatthe
momentaofthevariouselectronsarenotnecessarilypointinginthesamedirection.Iftwo
electronsarerevolvinginthesamedirectionaseachother,youwouldaddtheirlvalues.If
theywererevolvingoppositetoeachother,youwouldsubtractthem.Iftheyarerevolvingat
someoffanglerelativetoeachother,youwouldpartiallysubtractthem.
Tofigureoutallofthepossiblecombinationsoflforapairofelectrons,simplyaddthem
togethertogetthecoalignedcase,subtractthemtogettheopposingcase,andthenfillinall
thenumbersinbetweentogettheoffanglecases.Ifyouprefertohaveaformula,youcanuse
this:
L=|l1+l2|,|l1+l21|,,|l1l2|
Examples:WhatarethepossibleLvaluesfor1s22s22p2?
Bothopenshellelectronsarel=1.Thepossiblecombinationsare2,1,0
Whataboutconfiguration[Xe]6s24f15d1?
Wehaveanl=3andanl=2electron.3+2=5and32=1.Thepossiblecombinationsare
5,4,3,2,1
ThetotalmagneticquantumnumberMl
Mlisthetotalzcomponentofalloftherelevantelectronsorbitalmomentum.WhereLtold
youhowmuchangularmomentumtherewas,Mltellsyouwhichdirectionitispointing.LikeL,
agivenconfigurationcanhaveseveralpossiblevaluesofMl,dependingontheelectrons
relativeorientation.UnlikeL,Mlisallowedtohavenegativevalues(ifyouthinkcarefullyabout
whatLandMlmean,youwillseewhythisisthecase).TolistthepossibleMlvalues,takethe
casewherebothmlarepositive,thentakethecasewheretheyarebothnegative,andthenfill
inthenumbersinbetween.Heresaformula:Ml=ml1+ml2,ml1+ml21,,ml1ml2
Example:WhatarethepossiblevaluesMlof40[Kr]5s24d2?
Bothopenshellelectronsarel=2,sothevaluesare4,3,2,1,0,1,2,3,4
ThetotalspinmagneticquantumnumberMs
Msisthesumtotalofthezcomponentsoftheelectronsinherentspin.Donotconfuse
itwithMl,whichisthesumtotalofthezcomponentoftheorbitalangularmomentum.Itis
easilycomputedbyfindingallofthepossiblecombinationsofms.Sincemsforeachindividual
electroncanonlybe+1/2or1/2,thisisnttoocomplicated.
Ms=ms1+ms2,ms1+ms21,,ms1ms2
Example:WhataretheMsvaluesfor1s22s22p2?
Ms=1,0,1
ThetotalinherentspinquantumnumberS
ThesumtotalofthespinvectorsofalloftheelectronsiscalledS.Thedifference
betweenSandMsissubtlebutvitalforunderstandingmultiplicity.Msmeasuresthetotalz
componentoftheelectronsspins.Smeasurestheentireresultantvector.
ThevaluesofSarecomputinginamannerverysimilartoMs.BecauseSmeasuresthe
magnitudeofavector,itcannoteverbenegative.S=|s1+s2|,|s1+s21|,,|s1s2|
Examples:FindSfor1s1
Sclearlyhastobesincethatsthespinofasingleelectronandtheresonlyone
electrontoworryabout.
FindSfor1s22s12p1
S=1,0
FindSfor1s22s22p2
S=1,0 thesameasthepreviousproblem.NoticethatSisnotaffectedbywhich
orbitalstheelectronsarein.Sonlycaresabouthowmanyopenshellelectronsthereare,not
aboutwheretheyare.ThisisbecauseSmeasuresaninherentpropertyoftheelectrons
themselves.
FindSfor1s22s22p3
Wehaventdoneathreeelectroncaseyet,buttheyarenthard.Findallthe
combinationsforasinglepairfirst,andthenfactorinthethirdelectron.Fortwoelectrons,we
alreadyknowthatthetwopossibleSvaluesareS=1,0.Athirdelectroncaneitheraddor
subtractfromthesevalues,sothefinalSisS=3/2,1,1/2
ThetotalangularmomentumquantumnumberJ
Thetotalorbitalangularmomentumofanatom(measuredintermsofL),andthetotal
spinangularmomentumofanatom(measureinS)combinetoformtotalangularmomentum,
anumberthatisquantizedbythenumberJ.Landdonotnecessarilyhavetobepointinginthe
samedirection,soJcanrangefromL+Sto|LS|.
Symbol
L
Ml
Ms
S
M
J
Name
Totalorbital
angular
momentum
magnetic
quantum
spinmagnetic
quantum
number
Inherentspin
number
Multiplicity
Totalangular
momentum
AllowedRange
[|l1+l2|,|l1l2|]
[ml1+ml2,ml1ml2]
[|ms1+ms2|,|ms1ms2|]
[|s1+s2|,|s1s2|]
2S+1
[L+S,|LS|]
Interlude:Multiplicity
Multiplicityisasimplesoundingconceptthatdefiessimpleexplanations.Youknowfromyour
firstyeareducationthatasingletiswhenthenetspin(S)isequaltozero(e.g.alltheelectrons
arespinpaired),andatriplethappenswhenthenetspinisequalto1(e.g.twoelectronsare
pointinginthesamedirection).Theyarecalledsingletandtripletbecausethereare3ways
tocombineapairofelectronspinstogetS=1,butonlyonewaytogetS=0.
Ifyoudrawapictureofthepossiblewaysthattwoelectronscanarrangetheirspins,youget
somethinglikethis:
IfyouarelikemewhenIfirststudyingmultiplicity,youjustletoutanexasperatedsigh.Its
veryobviousthatthefirstandlastpairsshouldhaveS=1,butthetwomiddlepairsareanti
parallel.Shouldnttherebetwosingletstatesandtwotripletstates?Whyisoneofthemiddle
pairscountedasasingletandtheotheroneasatriplet?fpredicti
TheconfusionarisesfromtakingthePaulinotationtooliterally.Likewesawearlier,electrons
dontreallyaligntheirspinsupanddown.Theyalignthematangles.Whenwecallan
electronspinup,whatwereallymeanisthatithasapositivezcomponent(e.g.ms=+).
Whilethispictureisanimprovementoverthesimpleupdownmodel,itisstillmisleading.The
threespinaxesofanelectronshareaHeisenbergUncertaintyPrinciple.Themoreyouknow
aboutSx,thelessyoucanknowabouteitherSyorSz.Thesameistrueforallother
combinationsofx,yandz.SincewehavedefinedSzasaknownandfixedvalue,thevaluesof
SxandSymustbecompletelyunknown.Thiscausesthexandyorientationsoftheelectronsto
becomesmearedoutacrossallpossiblevalues:
Puttingitalltogether
Atomictermsymbolscontaintwopiecesofinformation.Theytellyouthetotalorbital
angularmomentumoftheatom(L),andtheytellyouthemultiplicity(M).Lisdenotedbya
simplecode,similartothecodeusedtodelineatethetypesofatomicorbitals:
L=0S
L=1P
L=2D
L=3F
Notethatwhilethenotationissimilar,LdoesNOTsayanythingaboutwhattypesoforbitals
theelectronsarein.AstatethathasthetermsymbolPdoesNOTnecessarilyhaveanopenp
shell.
Themultiplicityisindicatedbyappendinganumbertotheupperleftofthesymbol.A
L=2,M=3statewouldberepresentedby3D.Thesecrettowritingthetermsymbolsforan
atomistodiscoverwhatcombinationsofLandMarepossibleforthatatom.
Anatomthatonlyhasclosedshellswillalwaysbe1S.
Examples:Whatarethetermsymbolsfor1s1?
Sincethereisonlyoneelectron,thisisasimpleproblem.L=0andM=1,sotheonly
possibletermsymbolis2S.Withonlyoneelectron,S=,soJ=0+=.Thefinalterm
symbolis2S
Whatarethetermsymbolsfor1s22s22p1?
Therestillonlyoneopenshellelectron,soL=1,M=1andS=.Wegetatermsymbol
ofthetype2P,.whichgetssplitintoseparatesymbolsbecauseJ=3/2and.Theterm
symbolsare2P3/2and2P1/2
Whatabout1s22s12p1?
Nowwehavetwoelectronstoworryabout.Sincel1=0andl2=1,theonlypossible
combinationisL=1.ThepossiblecombinationsofSare:S=1,0.ThismeansthatM=3,1.The
termsymbolswillbeoftheform1Pand3P. Forthe1Pstate,L=1andS=0,soJ=1.Forthe
secondstate,L=1andS=1,soJ=2,1,0.Thefinaltermsymbolsare1P1and3P2,3P1,and3P0
Whatabout[Kr]5s24d2?
Thisisamuchharderproblem.Wewillneedtouseaspecialtechniquetodisentangle
allofthepossiblecombinationsofLandM.Letsstartbelistingtherelevantquantumnumbers
forthetwoelectrons:
l1=2
ml1=2,1,0,1,2
ms1=,
l2=2
ml2=2,1,0,1,2
ms2=,
Letscombinethesenumberstogeneratetheatomicquantumnumbers:
L=4,3,2,1,0
Ml=4,3,2,1,0,1,2,3,4
Ms=1,0
WeknowthattherewillatleastoneeachofS,P,D,FandG.Itisntimmiediatelyclearwhichof
thesewillbesingletsandwhichwillbetriplets.Tofigurethisout,weneedtosystematically
examinethepossiblemicrostates.Itturnsoutthatthereare45possiblewaystoputdistribute
twoelectronsbetween5dorbitals.Thatsalot!Theeasiestwaytolistthestatesistoorganize
themintoachart:
Ms
0
Irecommendattackingthechartonerowatatime.Askyourself,howmanywayscanIarrangethetwo
electronstogivemeMl=4?Itturnsoutthereisonlyonepossiblecombinationthatdoesthis:
ThisstateishasMs=0.Thismeansthatthereisonly1microstatethatcorrespondstoMl=4andMs=0,
andnonethatcorrespondtoMl=4andMs=+/1.Werepresentthisonthechartlikethis:
Ms
1
0
Now,howmanywaysaretheretogetMl=3?
1
0
1
Ms
0
1
2
1
0
1
ForMl=2,wefindthefollowingstates:
1
0
1
1
Ms
1
2
3
1
0
1
1
Ml=1:Youshouldbeabletodrawthemicrostatesonyourownbynow.Youshouldfind8
states,fourofwhicharesingletandfourofwhicharetriplets.
Ms
0
1
1
2
1
2
3
4
0
1
1
2
Ml=0ThereareonlyninepossiblewaystoarrangetheelectronstogetMl=0
Ms
1
0
1
1
2
2
0
1
2
3
4
5
1
0
1
1
2
2
Therestofthechartwillbesymmetrictothefirsthalf,sowedontneedtodoanymorework:
Ms
1
0
1
1
2
2
2
1
1
0
1
2
3
4
5
4
3
2
1
1
0
1
1
2
2
2
1
1
0
Nowthatwehavealistingofallofthemicrostates,weneedtofigureouthowtodividethem
upbetweenthetermsymbols.Itturnsoutthateachtermsymbolcanhave,atmost,one
microstatefromeachboxonthechart.Thetermsymbolsalwaysendupclaimingaboxof
microstates,centeredonthemiddleofthechart.Thisiseasiershownthansaid.
Attackingthechartfromthetop,IcanseethattheMl=4Ms=0stateclearlybelongsto
1
a Gsymbol.TheMl=4Ms=0boxalsoclearlybelongstothissymbol.IfIconnectthesestates
withabox,Igetthis:
Ms
0
1
1
2
2
2
1
1
0
1
2
3
4
5
4
3
2
1
1
0
1
1
2
2
2
1
1
0
Thecirclesstatedallbelongtothe1Gstate.Imgoingtosubtractthemoutofthechartto
indicatethattheyarentavailableforothertermsymbols.
1
1
Ms
0
1
1
1
1
2
2
2
1
1
2
3
4
3
2
1
1
2
2
2
1
1
ThenextrowindicatesaL=3state.BecausetherearethreeMsvaluesavailable,Iknow
thatitisatriplet.Thetermsymbolwillbe3Fandwilluseupthefollowingmicrostates:
1
1
2
2
2
1
1
Ms
1
2
3
4
3
2
1
1
1
2
2
2
1
1
1
2
3
2
1
0
1
1
1
0
Whichreducesthechartdownto
0
1
1
1
0
Thenextstatewillbe1D:
0
1
1
1
0
Ms
0
1
2
3
2
1
0
1
1
1
0
Leavinguswith
Ms
1
1
1
1
2
1
1
1
1
Nextisa3Pstate:
Ms
1
1
1
1
2
1
1
1
1
Thechartisgettingprettysmallnow:
Ms
0
Thelastremainingmicrostatecomprisesthe1Stermsymbol.Thetotallistingis1G,3F,1D,3P,1S.
AssigningJvalues,weget1G43F43F33F21D23P23P13P01S0
Ifyoucandothisproblem,youcandoalmostanyatomictermsymbol.
Shortcuts
Thereisadeepsymmetrythatconnectsdifferentelectronicconfigurations.Itturnsout
thatap1configurationhasthesametermsymbolsasap5.Similarly,p2=p4.Asimilar
relationshipcanbeusedtofigureouthighelectronnumbertermsymbolsforthedandf
orbitals.
Predictingenergylevels
Eachtermsymbolrepresentsadiscreteenergylevel.Wecanplacetheselevelsinthecorrectorderby
usingthesesimplerules:
1) Highmultiplicityvaluesmeanlowenergy
2)Ifthereisatie,highLvaluesmeanlowenergy
3a)Ifthereisstillatieandtheshellislessthanhalffull,thenlowJmeanslowenergy
3b)Iftheshellismorethanhalffull,thenhighJmeanslowenergy
Theserulesreliablypredictthegroundstate.Theyhaveonlyerraticagreementwithexperimentwhen
orderingtheotherlevels.
Molecularquantumnumbers
Thequantumnumbersfordiatomicmoleculesaresimilarfromtheatomicquantumnumbers.
Becautious,becausetherulesforfindingthepossiblecombinationsaredifferent.
Thetotalorbitalangularmomentumquantumnumber
Forthemolecularcase,thisnumberiscalledinsteadofL.Itfollowsthesamenaming
conventionasL,exceptthatinsteadofusingcapitalEnglishletters,itusescapitalGreekletters:
=0
=1
=2
=3
UnlikeL,thereisnotageneralformulaforfindingthepossiblecombinationsof.You
havetoexaminetheindividualmicrostates.Thisiseasierthanitsounds.
ThetotalmagneticquantumnumberML
MLworkslikeMl,exceptthatthereisnoformulaforfindingthecombinations.
ThetotalspinmagneticquantumnumberMS
MSworksexactlylikeMs.Electronscaneitherpointwithoragainstthezaxis,andbeing
inamolecularorbitalversusanatomicorbitaldoesntchangethis.MScanrangefrom
ms1+ms2toms1ms2
Twonewcomponents:parityandreflection
Molecularorbitalsaremorecomplexthanatomiconesandrequiremoremodifiersto
completelydefine.
Parity(sometimescalledinversion)tellsyouiftheorbitalissymmetricorantisymmetric
whenaninversionoperationisperformed.Symmetriccasesarecalledgerade.Anti
symmetriccasesarecalledungerade.Someexamples:
Thispiorbitalisgerade
Thispiorbitalisungerade
Todeterminewhetherornotagivenstateisgoru,findtheparityofeachindividualopenshell
electronandusesthesesimplerules:
g+gg
g+uu
u+ug
Example:Whatistheparityofthestate1g21u22g22u22u12u1?
Sincebothopenshellelectronsareungerade,theoverallparityisg.Helpfulhint:
bondingsigmaorbitalsandantibondingpiorbitalsarealwaysgerade.Antibondingsigmasand
bondingpisarealwaysungerade.Drawthemandseeforyourself.
Reflectiondeterminesifagivenorbitalissymmetricorantisymmetricuponreflectionthrough
aplanethatcontainsbothnuclei.Thechoiceofsymmetryplanesisarbitrary.Aslongasyou
pickaplaneandstickwithit,youwillalwaysgettherightanswer.Whenanorbitalis
symmetric,itislabeled+.Whenanorbitalisantisymmetric,itislabeled.Tofindtheoverall
reflectionofastate,usetheserules:
(+)(+)+
(+)()
()()+
Reflectiononlyappliestostates!For>0,therearenoreflectionlabels!Ifyouexperiment
withtherules,youwillquicklyrealizewhythisisthecase.
Example:Whatisthereflectionofthestate1g21u22g22u22u12u1?
Youneedtoknowwhattheorbitalslooklike.Drawapictureandthenpickaplane.For
thisexample,Illusetheplaneofthepage,buttheorthogonalplanewouldhaveworkedjustas
well.
Theverticalorbitalis+
Thehorizontalorbitalis
Sinceoneis+andoneis,theoverallreflectionis.Tryusingtheorthogonalplaneand
convinceyourselfthatyoustillgetthesameanswer.
Alltogethernow
WhatarethetermsymbolsforO2?
ThemolecularorbitaldiagramforOis:
WhereIchosearbitraryconfigurationsforthelasttwoelectrons.
Therearetwoopenshellelectronsoccupyingtheantibondinggorbitals.Theseare
theonlyelectronsthatmatter.Itiseasiesttosimplydrawallofthepermutationsandfigure
outtheboundsonandMLbyinspection.Ifwedothis,itiseasytoseethat=2,0andthat
ML=2,0,2
0
1
0
1
2
1
0
1
0
Thetoprowisa=2MS=0state,soitis1.Bothelectronsareintherightmost
orbital.Thisorbitalisgerade,and(g)(g)=g,sotheparitylabelisg.Wedonotassign
reflectionlabelstononstates,sothetermsymbolis1g
Afterremovingtheusedupmicrostates,thechartbecomes
1
0
1
2
1
Thisisa=0statewiththreepossiblespinconfigurations,soitis3.Weknow
thattheelectronsareindifferentsuborbitals(ifyoucantseethis,trydrawingallofthe
possiblecombinationsthatgive=0).Bothoftheorbitalsaregerade,sotheoverall
parityisgerade.Oneoftheorbitalswillbe+,theotherwillbe.Thefinalansweris
1
g3+g
WritethetermsymbolsforO2.
Drawthediagram.
Thereareonlytwopossibleconfigurations.Itshouldbeeasytoseethatthe
termsymbolis2g.