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QuantumNumbersandElectronConfigurations

QuantumNumbersandElectronConfigurations
Shellsand
Subshellsof
Orbitals

Table:
Possible
Summaryof
Combinations
Allowed
ofQuantum Combinations
Numbers
ofQuantum
Numbers

Quantum
Numbers

RulesGoverning
Quantum
Numbers

Relative
Energies
of
Atomic
Orbitals

Electron
Configurations,
Table:The
Exceptionsto
Electron
theAufbau
Electron
Predicted Configurations
Principle,
Configurations
Electron
andthe
Degenerate
ofthe
Configurations PeriodicTable
Orbitals,and
Elements
Hund'sRule
QuantumNumbers

TheBohrmodelwasaonedimensionalmodelthatusedonequantumnumbertodescribethedistributionofelectronsintheatom.Theonlyinformation
thatwasimportantwasthesizeoftheorbit,whichwasdescribedbythenquantumnumber.Schrdinger'smodelallowedtheelectrontooccupythree
dimensionalspace.Itthereforerequiredthreecoordinates,orthreequantumnumbers,todescribetheorbitalsinwhichelectronscanbefound.
ThethreecoordinatesthatcomefromSchrdinger'swaveequationsaretheprincipal(n),angular(l),andmagnetic(m)quantumnumbers.These
quantumnumbersdescribethesize,shape,andorientationinspaceoftheorbitalsonanatom.
Theprincipalquantumnumber(n)describesthesizeoftheorbital.Orbitalsforwhichn=2arelargerthanthoseforwhichn=1,forexample.Because
theyhaveoppositeelectricalcharges,electronsareattractedtothenucleusoftheatom.Energymustthereforebeabsorbedtoexciteanelectronfroman
orbitalinwhichtheelectronisclosetothenucleus(n=1)intoanorbitalinwhichitisfurtherfromthenucleus(n=2).Theprincipalquantumnumber
thereforeindirectlydescribestheenergyofanorbital.
Theangularquantumnumber(l)describestheshapeoftheorbital.Orbitalshaveshapesthatarebestdescribedasspherical(l=0),polar(l=1),or
cloverleaf(l=2).Theycaneventakeonmorecomplexshapesasthevalueoftheangularquantumnumberbecomeslarger.

Thereisonlyonewayinwhichasphere(l=0)canbeorientedinspace.Orbitalsthathavepolar(l=1)orcloverleaf(l=2)shapes,however,canpointin
differentdirections.Wethereforeneedathirdquantumnumber,knownasthemagneticquantumnumber(m),todescribetheorientationinspaceofa
particularorbital.(Itiscalledthemagneticquantumnumberbecausetheeffectofdifferentorientationsoforbitalswasfirstobservedinthepresenceofa
magneticfield.)

RulesGoverningtheAllowedCombinationsofQuantumNumbers
Thethreequantumnumbers(n,l,andm)thatdescribeanorbitalareintegers:0,1,2,3,andsoon.
Theprincipalquantumnumber(n)cannotbezero.Theallowedvaluesofnaretherefore1,2,3,4,andsoon.
Theangularquantumnumber(l)canbeanyintegerbetween0andn1.Ifn=3,forexample,lcanbeeither0,1,or2.
Themagneticquantumnumber(m)canbeanyintegerbetweenland+l.Ifl=2,mcanbeeither2,1,0,+1,or+2.

PracticeProblem7:
Describetheallowedcombinationsofthen,l,andmquantumnumberswhenn=3.
ClickheretocheckyouranswertoPracticeProblem7

ShellsandSubshellsofOrbitals
Orbitalsthathavethesamevalueoftheprincipalquantumnumberformashell.Orbitalswithinashellaredividedintosubshellsthathavethesamevalue
oftheangularquantumnumber.Chemistsdescribetheshellandsubshellinwhichanorbitalbelongswithatwocharactercodesuchas2por4f.Thefirst
characterindicatestheshell(n=2orn=4).Thesecondcharacteridentifiesthesubshell.Byconvention,thefollowinglowercaselettersareusedto
indicatedifferentsubshells.
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s:
p:
d:
f:

l=0
l=1
l=2
l=3

Althoughthereisnopatterninthefirstfourletters(s,p,d,f),thelettersprogressalphabeticallyfromthatpoint(g,h,andsoon).Someoftheallowed
combinationsofthenandlquantumnumbersareshowninthefigurebelow.

Thethirdrulelimitingallowedcombinationsofthen,l,andmquantumnumbershasanimportantconsequence.Itforcesthenumberofsubshellsina
shelltobeequaltotheprincipalquantumnumberfortheshell.Then=3shell,forexample,containsthreesubshells:the3s,3p,and3dorbitals.

PossibleCombinationsofQuantumNumbers
Thereisonlyoneorbitalinthen=1shellbecausethereisonlyonewayinwhichaspherecanbeorientedinspace.Theonlyallowedcombinationof
quantumnumbersforwhichn=1isthefollowing.
n

n
2

l
0

m
0

1s

Therearefourorbitalsinthen=2shell.

2s

2p

Thereisonlyoneorbitalinthe2ssubshell.But,therearethreeorbitalsinthe2psubshellbecausetherearethreedirectionsinwhichaporbitalcanpoint.
OneoftheseorbitalsisorientedalongtheXaxis,anotheralongtheYaxis,andthethirdalongtheZaxisofacoordinatesystem,asshowninthefigure
below.Theseorbitalsarethereforeknownasthe2px,2py,and2pzorbitals.

Therearenineorbitalsinthen=3shell.
n

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3s

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3p

3d

Thereisoneorbitalinthe3ssubshellandthreeorbitalsinthe3psubshell.Then=3shell,however,alsoincludes3dorbitals.
Thefivedifferentorientationsoforbitalsinthe3dsubshellareshowninthefigurebelow.OneoftheseorbitalsliesintheXYplaneofanXYZcoordinate
systemandiscalledthe3dxyorbital.The3dxzand3dyzorbitalshavethesameshape,buttheyliebetweentheaxesofthecoordinatesystemintheXZand
YZplanes.ThefourthorbitalinthissubshellliesalongtheXandYaxesandiscalledthe3dx2y2orbital.Mostofthespaceoccupiedbythefifthorbital
liesalongtheZaxisandthisorbitaliscalledthe3dz2orbital.

Thenumberoforbitalsinashellisthesquareoftheprincipalquantumnumber:12=1,22=4,32=9.Thereisoneorbitalinanssubshell(l=0),three
orbitalsinapsubshell(l=1),andfiveorbitalsinadsubshell(l=2).Thenumberoforbitalsinasubshellistherefore2(l)+1.
Beforewecanusetheseorbitalsweneedtoknowthenumberofelectronsthatcanoccupyanorbitalandhowtheycanbedistinguishedfromoneanother.
Experimentalevidencesuggeststhatanorbitalcanholdnomorethantwoelectrons.
Todistinguishbetweenthetwoelectronsinanorbital,weneedafourthquantumnumber.Thisiscalledthespinquantumnumber(s)becauseelectrons
behaveasiftheywerespinningineitheraclockwiseorcounterclockwisefashion.Oneoftheelectronsinanorbitalisarbitrarilyassignedansquantum
numberof+1/2,theotherisassignedansquantumnumberof1/2.Thus,ittakesthreequantumnumberstodefineanorbitalbutfourquantumnumbersto
identifyoneoftheelectronsthatcanoccupytheorbital.
Theallowedcombinationsofn,l,andmquantumnumbersforthefirstfourshellsaregiveninthetablebelow.Foreachoftheseorbitals,therearetwo
allowedvaluesofthespinquantumnumber,s.

Anappletshowingatomicandmolecularorbitalsfrom

SummaryofAllowedCombinationsofQuantumNumbers
Subshell
NumberofOrbitalsinthe
NumberofElectronsNeededtoFill
TotalNumberofElectronsin
n l m
Notation
Subshell
Subshell
Subshell

1 0 0
1s
1
2
2

2 0 0
2s
1
2
2 1 1,0,1
2p
3
6
8

3 0 0
3s
1
2
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3 1 1,0,1
3p
3
6
3 2 2,1,0,1,2
3d
5
10
18

4 0 0
4s
1
2
4 1 1,0,1
4p
3
6
4 2 2,1,0,1,2
4d
5
10
4 3 3,2,1,0,1,2,3
4f
7
14
32

TheRelativeEnergiesofAtomicOrbitals
Becauseoftheforceofattractionbetweenobjectsofoppositecharge,themostimportantfactorinfluencingtheenergyofanorbitalisitssizeandtherefore
thevalueoftheprincipalquantumnumber,n.Foranatomthatcontainsonlyoneelectron,thereisnodifferencebetweentheenergiesofthedifferent
subshellswithinashell.The3s,3p,and3dorbitals,forexample,havethesameenergyinahydrogenatom.TheBohrmodel,whichspecifiedtheenergies
oforbitsintermsofnothingmorethanthedistancebetweentheelectronandthenucleus,thereforeworksforthisatom.
Thehydrogenatomisunusual,however.Assoonasanatomcontainsmorethanoneelectron,thedifferentsubshellsnolongerhavethesameenergy.
Withinagivenshell,thesorbitalsalwayshavethelowestenergy.Theenergyofthesubshellsgraduallybecomeslargerasthevalueoftheangular
quantumnumberbecomeslarger.
Relativeenergies:s<p<d<f
Asaresult,twofactorscontroltheenergyofanorbitalformostatoms:thesizeoftheorbitalanditsshape,asshowninthefigurebelow.

Averysimpledevicecanbeconstructedtoestimatetherelativeenergiesofatomicorbitals.Theallowedcombinationsofthenandlquantumnumbersare
organizedinatable,asshowninthefigurebelowandarrowsaredrawnat45degreeanglespointingtowardthebottomleftcornerofthetable.

Theorderofincreasingenergyoftheorbitalsisthenreadoffbyfollowingthesearrows,startingatthetopofthefirstlineandthenproceedingontothe
second,third,fourthlines,andsoon.Thisdiagrampredictsthefollowingorderofincreasingenergyforatomicorbitals.
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d<7p<8s...

ClickhereforExtraPracticeProblems

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ElectronConfigurations,theAufbauPrinciple,DegenerateOrbitals,andHund'sRule
Theelectronconfigurationofanatomdescribestheorbitalsoccupiedbyelectronsontheatom.Thebasisofthispredictionisaruleknownastheaufbau
principle,whichassumesthatelectronsareaddedtoanatom,oneatatime,startingwiththelowestenergyorbital,untilalloftheelectronshavebeen
placedinanappropriateorbital.
Ahydrogenatom(Z=1)hasonlyoneelectron,whichgoesintothelowestenergyorbital,the1sorbital.Thisisindicatedbywritingasuperscript"1"after
thesymbolfortheorbital.
H(Z=1):1s1
Thenextelementhastwoelectronsandthesecondelectronfillsthe1sorbitalbecausethereareonlytwopossiblevaluesforthespinquantumnumber
usedtodistinguishbetweentheelectronsinanorbital.
He(Z=2):1s2
Thethirdelectrongoesintothenextorbitalintheenergydiagram,the2sorbital.
Li(Z=3):1s22s1
Thefourthelectronfillsthisorbital.
Be(Z=4):1s22s2
Afterthe1sand2sorbitalshavebeenfilled,thenextlowestenergyorbitalsarethethree2porbitals.Thefifthelectronthereforegoesintooneofthese
orbitals.
B(Z=5):1s22s22p1
Whenthetimecomestoaddasixthelectron,theelectronconfigurationisobvious.
C(Z=6):1s22s22p2
However,therearethreeorbitalsinthe2psubshell.Doesthesecondelectrongointothesameorbitalasthefirst,ordoesitgointooneoftheother
orbitalsinthissubshell?
Toanswerthis,weneedtounderstandtheconceptofdegenerateorbitals.Bydefinition,orbitalsaredegeneratewhentheyhavethesameenergy.The
energyofanorbitaldependsonbothitssizeanditsshapebecausetheelectronspendsmoreofitstimefurtherfromthenucleusoftheatomastheorbital
becomeslargerortheshapebecomesmorecomplex.Inanisolatedatom,however,theenergyofanorbitaldoesn'tdependonthedirectioninwhichit
pointsinspace.Orbitalsthatdifferonlyintheirorientationinspace,suchasthe2px,2py,and2pzorbitals,arethereforedegenerate.
ElectronsfilldegenerateorbitalsaccordingtorulesfirststatedbyFriedrichHund.Hund'srulescanbesummarizedasfollows.
Oneelectronisaddedtoeachofthedegenerateorbitalsinasubshellbeforetwoelectronsareaddedtoanyorbitalinthesubshell.
Electronsareaddedtoasubshellwiththesamevalueofthespinquantumnumberuntileachorbitalinthesubshellhasatleastoneelectron.
Whenthetimecomestoplacetwoelectronsintothe2psubshellweputoneelectronintoeachoftwooftheseorbitals.(Thechoicebetweenthe2px,2py,
and2pzorbitalsispurelyarbitrary.)
C(Z=6):1s22s22px12py1
Thefactthatbothoftheelectronsinthe2psubshellhavethesamespinquantumnumbercanbeshownbyrepresentinganelectronforwhichs=+1/2
withan
arrowpointingupandanelectronforwhichs=1/2withanarrowpointingdown.
Theelectronsinthe2porbitalsoncarboncanthereforeberepresentedasfollows.

WhenwegettoN(Z=7),wehavetoputoneelectronintoeachofthethreedegenerate2porbitals.
N(Z=7): 1s22s22p3
Becauseeachorbitalinthissubshellnowcontainsoneelectron,thenextelectronaddedtothesubshellmusthavetheoppositespinquantumnumber,
therebyfillingoneofthe2porbitals.
O(Z=8): 1s22s22p4
Theninthelectronfillsasecondorbitalinthissubshell.
F(Z=9): 1s22s22p5
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Thetenthelectroncompletesthe2psubshell.
Ne(Z=10): 1s22s22p6
Thereissomethingunusuallystableaboutatoms,suchasHeandNe,thathaveelectronconfigurationswithfilledshellsoforbitals.Byconvention,we
thereforewriteabbreviatedelectronconfigurationsintermsofthenumberofelectronsbeyondthepreviouselementwithafilledshellelectron
configuration.Electronconfigurationsofthenexttwoelementsintheperiodictable,forexample,couldbewrittenasfollows.
Na(Z=11):[Ne]3s1
Mg(Z=12):[Ne]3s2
PracticeProblem8:
Predicttheelectronconfigurationforaneutraltinatom(Sn,Z=50).
ClickheretocheckyouranswertoPracticeProblem8
Theaufbauprocesscanbeusedtopredicttheelectronconfigurationforanelement.Theactualconfigurationusedbytheelementhastobedetermined
experimentally.Theexperimentallydeterminedelectronconfigurationsfortheelementsinthefirstfourrowsoftheperiodictablearegiveninthetablein
thefollowingsection.
LearningActivity

ClickhereforExtraPracticeProblems

TheElectronConfigurationsoftheElements
(1st,2nd,3rd,and4thRowElements)
AtomicNumber

Symbol

ElectronConfiguration

1
H
1s1
2

He

1s2=[He]

Li

[He]2s1

Be

[He]2s2

[He]2s22p1

[He]2s22p2

[He]2s22p3

[He]2s22p4

[He]2s22p5

10

Ne

[He]2s22p6=[Ne]

11

Na

[Ne]3s1

12

Mg

[Ne]3s2

13

Al

[Ne]3s23p1

14

Si

[Ne]3s23p2

15

[Ne]3s23p3

16

[Ne]3s23p4

17

Cl

[Ne]3s23p5

18

Ar

[Ne]3s23p6=[Ar]

19

[Ar]4s1

20

Ca

[Ar]4s2

21

Sc

[Ar]4s23d1

22

Ti

[Ar]4s23d2

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23

[Ar]4s23d3

24

Cr

[Ar]4s13d5

25

Mn

[Ar]4s23d5

26

Fe

[Ar]4s23d6

27

Co

[Ar]4s23d7

28

Ni

[Ar]4s23d8

29

Cu

[Ar]4s13d10

30

Zn

[Ar]4s23d10

31

Ga

[Ar]4s23d104p1

32

Ge

[Ar]4s23d104p2

33

As

[Ar]4s23d104p3

34

Se

[Ar]4s23d104p4

35

Br

[Ar]4s23d104p5

36

Kr

[Ar]4s23d104p6=[Kr]

ExceptionstoPredictedElectronConfigurations
Thereareseveralpatternsintheelectronconfigurationslistedinthetableintheprevioussection.Oneofthemoststrikingistheremarkablelevelof
agreementbetweentheseconfigurationsandtheconfigurationswewouldpredict.Thereareonlytwoexceptionsamongthefirst40elements:chromium
andcopper.
Strictadherencetotherulesoftheaufbauprocesswouldpredictthefollowingelectronconfigurationsforchromiumandcopper.
predictedelectronconfigurations: Cr(Z=24):[Ar]4s23d4
Cu(Z=29):[Ar]4s23d9
Theexperimentallydeterminedelectronconfigurationsfortheseelementsareslightlydifferent.
actualelectronconfigurations: Cr(Z=24):[Ar]4s13d5
Cu(Z=29):[Ar]4s13d10
Ineachcase,oneelectronhasbeentransferredfromthe4sorbitaltoa3dorbital,eventhoughthe3dorbitalsaresupposedtobeatahigherlevelthanthe
4sorbital.
Oncewegetbeyondatomicnumber40,thedifferencebetweentheenergiesofadjacentorbitalsissmallenoughthatitbecomesmucheasiertotransferan
electronfromoneorbitaltoanother.Mostoftheexceptionstotheelectronconfigurationpredictedfromtheaufbaudiagramshownearlierthereforeoccur
amongelementswithatomicnumberslargerthan40.Althoughitistemptingtofocusattentiononthehandfulofelementsthathaveelectron
configurationsthatdifferfromthosepredictedwiththeaufbaudiagram,theamazingthingisthatthissimplediagramworksforsomanyelements.

ElectronConfigurationsandthePeriodicTable
Whenelectronconfigurationdataarearrangedsothatwecancompareelementsinoneofthehorizontalrowsoftheperiodictable,wefindthattheserows
typicallycorrespondtothefillingofashelloforbitals.Thesecondrow,forexample,containselementsinwhichtheorbitalsinthen=2shellarefilled.
Li(Z=3):

[He]2s1

Be(Z=4):

[He]2s2

B(Z=5):

[He]2s22p1

C(Z=6):

[He]2s22p2

N(Z=7):

[He]2s22p3

O(Z=8):

[He]2s22p4

F(Z=9):

[He]2s22p5

Ne(Z=10): [He]2s22p6
Thereisanobviouspatternwithintheverticalcolumns,orgroups,oftheperiodictableaswell.Theelementsinagrouphavesimilarconfigurationsfor
theiroutermostelectrons.Thisrelationshipcanbeseenbylookingattheelectronconfigurationsofelementsincolumnsoneithersideoftheperiodic
table.
GroupIA

GroupVIIA

1s1

Li

[He]2s1 F
[Ne]3s1 Cl

Na

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[He]2s22p5
[Ne]3s23p5
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[Ar]4s1 Br

[Ar]4s23d104p5

Rb

[Kr]5s1

[Kr]5s24d105p5

Cs

[Xe]6s1 At

[Xe]6s24f145d106p5

Thefigurebelowshowstherelationshipbetweentheperiodictableandtheorbitalsbeingfilledduringtheaufbauprocess.Thetwocolumnsontheleft
sideoftheperiodictablecorrespondtothefillingofansorbital.Thenext10columnsincludeelementsinwhichthefiveorbitalsinadsubshellarefilled.
Thesixcolumnsontherightrepresentthefillingofthethreeorbitalsinapsubshell.Finally,the14columnsatthebottomofthetablecorrespondtothe
fillingofthesevenorbitalsinanfsubshell.
Diagram

PracticeProblem9:
Predicttheelectronconfigurationforcalcium(Z=20)andzinc(Z=30)fromtheirpositionsintheperiodictable.
ClickheretocheckyouranswertoPracticeProblem9

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