BohrModelCalculationsforAtomsandIons

FrankRioux
DepartmentofChemistry
CollegeofSt.Benedict|St.JohnsUniversity
St.Joseph,MN56374
Abstract
AdeBroglieBohrmodelisdescribedthatcanbeusedtocalculatetheelectronic
energiesofatomsorionscontaininguptofourelectrons.Sevenexercisesare
providedwhichcanbeusedtogivestudentstrainingindoingenergyaudits,
carryingoutsimplevariationalcalculationsandcriticallyanalyzingthe
calculatedresults.
Thisnotebuildsontwopublicationsinthepedagogicalliterature[1,2]thatshowedhow
extendingtheBohrmodeltotwoandthreeelectronatomsandionscouldbeusedtoenhance
studentunderstandingofatomicstructure.ABohrmodel,morecorrectlyadeBroglieBohrmodel,
isusedheretocalculatethetotalelectronicenergiesofatomsandionscontaininguptofour
electrons.
TheBohrmodelforthehydrogenatomistheprototypeofthesemiclassicalapproachtoatomic
andmolecularstructure.Althoughitwassupersededbyquantummechanicsmanydecadesago,
itisstilltaughttodaybecauseofitssimplicityandbecauseitintroducedseveralimportant
quantummechanicalconceptsthathavesurvivedthemodel:quantumnumber,quantizedenergy,
andquantumjump.
Whenappliedtomultielectronatomsandions,theBohrmodelprovidesapedagogicaltoolfor
improvingstudentsanalyticalandcriticalskills.Aswillbedemonstrated,givenapictureofan
atomorion,itisnotunrealistictoexpectanundergraduatestudenttoidentifyallthe
contributionstothetotalelectronicenergy,carryoutanenergyminimizationandinterpretthe
resultsinavarietyofways.Sevenstudentexercises,withanswers,areprovidedtoillustratehow
thismightbeaccomplished.
WebeginwithareviewofthedeBroglieBohrmodelforthehydrogenatom.Workinginatomic
units(h=2,me=e=40=1),andusingthedeBroglieBohrrestrictiononelectronorbits
(n=2Rn,wheren=1,2,3,...),thedeBrogliewaveequation(=h/mv)andCoulombslawthe
totalelectronenergyisthefollowingsumofitskineticandpotentialenergycontributions.
2

En =

2 Rn

1
Rn

MinimizationoftheenergywithrespecttothevariationalparameterR nyieldstheallowedorbit
radiiandenergies.
2

Rn = n a0

En =

0.5 E h
2

wherea0=52.9pmandEh=4.36x1018joule.
Themodelshowninthefigurebelowisfortheberylliumatomoranyfourelectronion.Note
thattheoccupancyoftheinnerorbitisrestrictedtotwoelectrons(PauliPrinciple)andthatthe
orbitradiiareconstrainedbythehydrogenatomresult(R 2=4R1)leavingonlyonevariational
parameter,theradiusofthen=1orbit.

Withthesemodelelementsandalittlegeometry[2]itiseasytospecifythekineticandpotential
energycontributionstothetotalenergy.Thenumericsubscriptsrefertothequantumnumberof
theorbit.ThusT1isthekineticenergyofanelectroninthen=1orbit,VN1isthepotentialenergy
interactionofanelectroninthen=1orbitwiththenucleus,andV 12isthepotentialenergy
interactionofanelectroninthen=1orbitwithanelectroninthen=2orbit.
TherecommendedstudentcalculationsdescribedbelowarecarriedoutintheMathcad
programmingenvironment[3].AMathcadfilefordoingtheexercisesisavailablefordownloadon
theInternet[4].Thecalculationfortheberylliumatomiscarriedoutasshownbelow.Required
studentinputisindicatedbythehighlightedregions.

Enternuclearcharge:

Z := 4

Kineticenergy:

Electronnucleuspotentialenergy:

Z
VN1 R1 :=
R1

Electronelectronpotentialenergy:

1
V11 R1 :=
2 R1

( )

( )

( )

T1 R1 :=

1
2 R1

( )

T2 R1 :=

1
8 R1

Z
VN2 R1 :=
4 R1

( )

( )

1
V22 R1 :=
8 R1

( )

V12 R1 :=

1
17 R1

Thenextstepistodoanenergyauditfortheatomorionunderconsideration.Thestudentis
promptedtoweighteachofthecontributionstothetotalelectronicenergy.Theentriesgiven
belowareappropriatefortheBohrberylliumatomshowninthefigureabove.
Entercoefficientsforeachcontributiontothethetotalenergy:

( )

T1 R1

a := 2

( )

VN1 R1

VN2 R1

V11 R1

V22 R1

V12 R1

b := 2

c := 2

d := 2

e := 1

f := 1

g := 4

T2 R1

( )

( )

( )

( )

( )

TheenergyoftheBohratom/ionintermsofthevariationalparameterR1,theradiusoftheinner
electronorbit,andthevariouskineticandpotentialenergycontributionsis:

( )

( )

( )

( )

( )

( )

( )

( )

E R1 := a T1 R1 + b T 2 R1 + c VN1 R1 + d VN2 R1 + e V11 R1 + f V22 R1 + g V12 R1

MinimizationoftheelectronicenergyoftheBohratom/ionwithrespecttoR 1yieldstheoptimum
innerorbitradiusandgroundstateenergy.

R1 :=

( )

d
E R1 = 0
dR1

solve , R1
.29744
float , 5

( )

E R1 = 14.128

Thus,thismodelpredictsastableberylliumatomwithanelectronicenergyinerrorbylessthan
4%.However,itmustbestressedthatthemainpurposeoftheexercisespresentedisnotto
promotetheBohrmodelassuch,buttouseitasavehicleforprovidingstudentswithtrainingin
doingenergyaudits,carryingoutsimplevariationalcalculationsandcriticallyanalyzingthe
calculatedresults.
Inthestudentexercisescriticalanalysiswillinvolveassessingthelevelofagreementwith
experimentalresults,andwhetherornotthevariationalprincipleandthevirialtheoremare
satisfied.Becausethesecondexerciseinvolvesthevirialtheoremascriterionforvalidity,itis
recommendedthatthefirstandsecondexercisesbedoneintandem.
StudentExercises
Exercise1:UsethisworksheettocalculatethegroundstateenergyforH,He,LiandBe,and
confirmalltheentriesinthetablebelow.Theexperimentalgroundstateenergyofanatomisthe
negativeofthesumofthesuccessiveionizationenergiesgiveninthedatatableintheAppendixA.

Element

He
Li
Be

E ( calc )

E ( exp)

Eh

Eh

0.500

0.500

3.062

2.904

7.385

7.480

14.128 14.672

%Error

5.46
1.26

3.71

Thisassignmentshowsthat,givenitssimplicity,theBohrmodelachievesacceptableresults.
However,thestudentsshouldnotethattheHeresultviolatesthevariationaltheorem.Inother
words,thecalculatedenergyislowerthantheexperimentalenergy.
Exercise2:Animportantcriterionforthevalidityofaquantummechanicalcalculationis
satisfyingthevirialtheoremwhichforatomsandionsrequires:E=T=V/2.Demonstratewhether
ornotthevirialtheoremissatisfiedfortheelementsinthefirstexercise.

( )

( )

( )

Calculatekineticenergy:

T R1 := a T1 R1 + b T 2 R1

Calculatepotentialenergy:

V R1 := E R1 T R1

( )

( )

T R1 = 14.129

( )

( )

Element

He
Li
Be

E ( calc )
Eh

T ( calc )
Eh

V ( calc )
2 Eh

0.500

0.500

0.500

Yes

3.062

3.062

3.602

Yes

7.385

7.385

7.385

Yes

14.128

14.129

14.129

Yes

( )

V R1

( )

V R1 = 28.257

= 14.129

VTSatisfied

TheBohrmodelsatisfiesthevirialtheoremforallatomiccalculations(atomsandions).Thisdoes
notguaranteethevalidityofthemodel.However,anymodelcalculationthatviolatesthevirial
theoremindicatesthatthemodelisnotquantummechanicallyvalid.
Exercise3:Plotthetotalenergy,andthekineticandpotentialenergycomponentsonthesame
graphforberylliumandinterprettheresults.
R1 := 0 , .01 .. 2

( )
T( R 1 )
0
V( R1 )
E R1

0.5

1.5

R1

Thisgraphclearlyshowsthatatomicstabilityistheresultoftwocompetingenergyterms.The
attractivecoulombicpotentialenergyinteractiondrawstheelectronstowardthenucleus.Atlarge
R1valuesthistermdominatesandtheelectronorbitsgetssmaller.However,thisattractive
interactionisovercomeatsmallR 1valuesbytherepulsivecharacterofkineticenergytermthat
dominatesatsmallR1valuesandanenergyminimum,agroundstateisachieved.

Exercise4:Calculatethegroundstateenergiesofsomecations(He +,Li+,Be+, B +,C2+)andcompare

yourcalculationswithexperimentalresultsusingthedatatableinAppendixA.

Cation

He1

Li1

Be1
1
B
2
C

E ( calc)
Eh

E ( exp)
Eh

2.000

2.000

7.562

7.282

3.70

14.275 14.329

0.38

23.782 24.348

2.33

35.938 36.613

1.88

%Error

Justasinthefirstexercise,theoneelectronspeciesHe +1isinexactagreementwithexperimentand
thetwoelectronion,Li+,violatesthevariationaltheorem.
Exercise5:Usetheresultsofexercises1and3tocalculatethefirstionizationenergiesofH,He,Li
andBeandcompareyourresultswiththeexperimentaldataavailableinAppendixA.

Element E ( atom) E ( ion) IE ( calc) IE ( exp)

Eh
Eh
Eh
Eh

H
0.500
0
0.500
0.500

3.063
2.000
1.063
0.904
He
Li
7.385
7.562
0.177
0.198
Be
14.128 14.275 0.147
0.343

TheresultsforHandHeareacceptable,butbothLiandBehavenegativeionizationenergies.
Exercise6:AretheanionsofH,HeandListable?Inotherwords,dotheyhaveenergieslower
thantheneutralspecies?

Anion Eion ( calc) Eatom( exp) Stable

Eh
Eh

Yes
0.562
0.500
H
1

No
2.745
2.904
He

Li 1

No
6.681
7.480

TheBohrmodelgetstheseresultscorrect.However,itshouldbenotedthatLi 1isstableinliquid
ammonia.

Exercise7:Doatwoparametervariationalcalculationontheberylliumatomshowninthe
Figure.Inotherwords,minimizethetotalelectronicenergyofaberylliumatomthathastwo
electronsinanorbitofradiusR1andtwoelectronsinanotherorbitofradiusR 2.
AsoutlinedinAppendixBthiscalculationyieldsthefollowingresults:R 1=R2=0.329a0and
E(R1,R2)=18.518Eh,anenergysignificantlylowerthancalculatedforberylliuminExercise1
Thus,intheabsenceoftheorbitaloccupancyrestrictionoftheexclusionprinciple,energy
minimizationplacesallelectronsinthegroundstateorbit.Itwasarealizationofthisthatlead
Pauliinparttoformulatetheexclusionprinciple.
Insummary,thepurposeofthisnoteistousetheBohrmodelasaninitialvehicletohelpstudents
developskillincarryingoutbasicatomicstructurecalculationsandtocriticallyanalyzetheresults
ofthosecalculations.

AppendixA
Data:SuccessiveIonizationEnergiesfortheFirstSixElements

Element

H
He

Li
Be
B

IE1

IE2

IE3

0.500

0.904 2.000

0.198 2.782 4.500

0.343 0.670 5.659
0.305 0.926 1.395
0.414 0.896 1.761

x
x
x
x
x
x

x
x
x

8.000
x
x
9.527 12.500
x

2.370 14.482 18.000

IE4

IE5

IE6

AppendixB
EnergycontributionsforthetwoparameterBohrcalculation:

( )

T1 R1 :=

( )

1
2 R1

T2 R2 :=

( )

1
V11 R1 :=
2 R1

( )

( )

1
2 R2

( )

1
V22 R2 :=
2 R2

( )

Z
VN1 R1 :=
R1

Z
VN2 R2 :=
R2

( )
(

V12 R1 , R2 :=

( )

( )

( )

1
2

R1 + R2

( )

E R1 , R2 := 2 T 1 R1 + 2 T2 R2 + 2 VN1 R1 + 2 VN2 R2 + V11 R1 + V22 R2 + 4 V12 R1 , R2

MinimizationoftheelectronicenergywithrespecttoR1andR2:

R1
:=
R2

1

4

R1
:= Minimize ( E , R1 , R2)
R2

R1 0.329
=
R2 0.329

E R1 , R2 = 18.518

Literaturecited:
1. Bagchi,B.;Holody,P.AninterestingapplicationofBohrtheory,Am.J.Phys.1988,56,746.
2. SalehJahromi,A.GroundStateEnergyofLithiumandLithiumlikeAtomsUsingtheBohr
Theory,TheChemicalEducator,2006,11,333334.
3. MathcadisaproductofMathsoft,101MainStreet,Cambridge,MA02142
4. http://www.users.csbsju.edu/~frioux/stability/BohrAtoms.mcd