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THE

THEORYOFATOMICSPECTRA

THE

THEORYOFATOMICSPECTRA

by

E.U.CONDON,PH.D.

WAYMANCROWFEOFB8SOEOPPHYSIOS,WASHINGTONXTNIVEBSITY

8TLOUIS,MISSOUEI

and

G.H.SHORTLEY,PH.D.

DIKECtOK,WASHINGTONOFEKATION8

BOOZ,ALLENAFFUKDEBSBABCHiINC,

CAMBRIDGE

ATTHEUNIVERSITYPEESS

1959

TUB

PUBLISHEDBY

SYNDICSOFTHEGAMBBIDGKUNIVERSITYPRKSS

BentleyHouse,200EustonRoad,London,N.W.I

American,Branch:32East57th8trootNowYork22,N,Y.

JPirttprinted

Reprintedwith

corrections

Reprinted

1936 1953

1051

1057

1050

First

printedbyinGreatBritainattheUniversity/Vaw,Oambrulge

offtet-lithobyBradforddbDic,kem>London,W.CLl

Reprinted

To

HENRYNOEBISRUSSELL

;,.;;,r.Na

630896*

-Ycm^mm,if;

Preface

CONTENTS

...........

CHAPTERI

INTRODUCTION ....

PAGE

xiii

1

CHAPTERII

SECTION

THEQUANTUMMECHANICALMETHOD

.

12

22

32

42

52

62

Symbolicalgebraofstatesandobservable

Representationsofstatesandobservables

.

.

. .

.

.

.

.

ContinuouseigenvaluesandtheSehrodingerrepresentation .

Thestatisticalinterpretation .

.

.

.

.

Thelawsofquantummechanics

.

.

Schrodingersequation........

  • 72 Matrixmechanics

82

II2 Perturbationtheory Perturbationcausedbyasinglestate

1C2 R6sum6oftheperturbationtheory Remarksontheperturbationtheory

92

122 Theanalysisofnon-commutingvectors

CHAPTERIII

ANGULARMOMENTUM

...

13 Definitionofangularmomentum

23 33 Allowedvaluesofangularmomentum Thematricesofangularmomentum

  • 43 Orbitalangularmomentum

5s Spinangularmomentum

6s Vectoradditionofangularmomenta

73

83

93

10s

Thematrixof(Ji+J,) 8

MatrixofTinthejmscheme.Selectionruleonj...

DependenceofthematrixofTonm

Thematricesof/!and/2? where/i+/2=J....

12

12

15

20

24

25

26

27

30

34

35

37

43

45

45

48 46

50

54

56 59 64

58

61

viii

CONTENTS

CHAPTERIII(continued)

SECTION

113

MatrixofavectorPwhichcommuteswithJ

  • 123 MatrixofP-Q

13s Sumrules

14s Transformationamplitudesforvectoraddition

...

...

PAGJD

67

70

71

73

CHAPTERIV

THETHEORYOFRADIATION

  • 14 Transitionprobabilities

  • 24 Classicalelectromagnetictheory

  • 34 Expansionoftheretardedpotential

4* Thecorrespondenceprincipleforemission

  • 54 Thedipole-radiationfield

  • 64 Thequadrupoie-radiationfield

  • 74 Spectrallinesinnaturalexcitation

  • 84 Inducedemissionandabsorption

  • 94 Dispersiontheory.Scattering.Ramaneffect.

t

.

104 Naturalshapeofabsorptionlines

.

.

.

.

79 83

79

84

87

90

93

97

100

103

109

CHAPTERV

ONE-ELECTRONSPECTRA

  • 15 Central-forceproblem

  • 25 Radialfunctionsforhydrogen

  • 35 Therelativitycorrection

  • 45 Spin-orbitinteraction

  • 55 Sketchoftherelativistictheory

6s 75 85 Intensitiesinhydrogen 9s Intensitiesinalkalispectra

Experimentalresultsforhydrogenicspectra .

Generalstructureofthealkalispectra

...

112

112

114

.

.

118

125 120

131

.147 .137

141

SECTION

CONTENTS

CHAPTERVI

ix

PAGE

THECENTRAL-FIELDAPPROXIMATION . 158

16

TheHamiltonianformany-electronatoms

.

.

.

.158

  • 26 Equivalencedegeneracy

 

160

  • 36 Thedynamicalequivalenceoftheelectrons .

 

.

.

.162 .166

46

ThePauHexclusionprinciple .

.

.

.

.

.

  • 56 Conventionsconcerningquantumnumbers.Closedshells

 

.

168

  • 66 MatrixcomponentsforS^gf(i,^) MatrixcomponentsforS^/(i)

76

 

169

171

  • 86 Matrixcomponentsofelectrostaticinteraction

 

.

.

.

174

  • 96 Specializationforclosedshells

 

177

1C6 Oneelectronoutsideclosedshells

183

II6 Oddandevenstates

185

CHAPTERVII

THERUSSELL-SAUNDERSCASE;ENERGYLEVELS 187

  • 17 TheJD/S-couplingscheme

  • 27 Termenergies

.

  • 37 TheLand6intervalrule

  • 47 Absolutetermintervals

  • 57 Formulasandexperimentalcomparison

  • 67 Termsinthenlxconfigurations

  • 77 Thetriplettermsofhelium .

CHAPTERVIII

188

191

193

207 195

197

210

THERUSSELL-SAUNDERSCASE:EIGENFUNCTIONS 213

  • 18 Vectorcouplinginantisymmetricstates.

.

.

.213

  • 28 Genealogicalcharacterizationofi/S-couplingterms

 

.

.

216

  • 38 Land6intervalsfortermsofcoupledgroups .

 

.

.

.219

48

Calculationofeigenfunctionsbydirectdiagonalization .

.

220

  • 58 Calculation of eigenfunctions using angular-momentum

 

operators

228 226

6s Calculationofeigenfunctionsfromvector-couplingformulas .

S:

CONTENTS

CHAPTERIX

PAGE

THERUSSELL-SAUNDERSCASE:LINESTRENGTHS 236

SECTION LinestrengthsinRussell-Saundersmultiplets

P Configurationselectionrules

29

...

  • 39 Multipletstrengthsinatransitionarray Multipletstrengthsobtainedfromspectroscopicstability

49

59 Quadrupoleniultiplets

.

CHAPTERX

jjCOUPLING

....

110 Thejj-couplingschemeandthespin-orbitinteraction .

210 Theadditionofaweakelectrostaticinteraction .

  • 310 Eigenfunctions

  • 410 Linestrengths

.

.

.

244 236

237

252 249

257

257

259

262

264

CHAPTERXI

INTERMEDIATECOUPLING...

  • 111 Matrixofspin-orbitinteractionforconfigurationsconsisting functions

ofcoupledgroups

2nMatrixofspin-orbitinteractionobtainedfromtheeigen-

266

266

270

311 IllustrationsofthetransitionfromLStojjcoupling

411 Linestrengthsinintermediatecoupling

.

511

Theforbiddenlinesofastrophysicalinterest .

, .

.

.

.

.

271

.277

.

282

CHAPTERXII

TRANSFORMATIONSINTHETHEORY

OPCOMPLEXSPECTRA

  • 112 Configurationscontainingalmostclosedshells

.

  • 212 ThetransformationtoLScoupling

  • 412 312 512 Thetransformationtojjcoupling Thetransformationbetweenzero-orderstates Thetransformationnlm8ml*=?nljm

.

...

.

.

.

.

284

284

285

287

287

290

CONTENTS

XI

CHAPTERXIII

CONFIGURATIONSCONTAININGALMOST

PAGE

SECTION

295

  • 113 TheelectrostaticenergyinLScoupling

 

295 300

299

  • 213 Thespin-orbitinteraction

 
  • 313 Purealmost-closed-shellconfigurations.....

 
  • 413 513 Therare-gasspectra Theconfigurationsp*sandd*$

  • 613 Theconfigurationp*pintheraregases

 

301

304

316 306

312

  • 713 Theconfiguration^ 5^intheraregases

  • 813 Linestrengths

  • 913 X-rayspectra

 

316

1013 LinestrengthsinX-rayspectra

 

322 323

II13 X-raysatellites

 

CHAPTERXIV

114

Theperiodicsystem

327 327

  • 214 ThestatisticalmethodofFermi-Thomas

 

335

3MTheWentzel-Brillouin-Kramersapproximation

.

 

.

.

339

  • 414 Numericalintegrationoftheradialequation....

344

  • 514 Normalstateofhelium

 

345

  • 614 Excitedlevelsinhelium

348 354

351

358 362

  • 714 814 Normalstatesoffirst-rowatoms Hartreesself-consistentfields

  • 914 Surveyofconsistent-fieldresults

 

1014 Self-consistentfieldsforoxygen

 

CHAPTERXV

 

CONFIGURATIONINTERACTION .

 

.

365

  • 115 Interactionofsdand# 2inmagnesium

 

366

  • 215 Perturbedseries

 

367

  • 315 Auto-ionization

369

  • 415 Many-electronjumps

.

375 376

  • 515 Spin-orbitperturbationofdoubletintensities

.

.

Xll

SEOTION

CONTENTS

CHAPTERXVI

THEZEEMANEFFECT

  • 116 ThenormalZeemaneffect

...

  • 216 Theweak-fieldcase: Eussell-Saundersterms....

  • 316 Weakfields: generalcase

PAGE

378

378

380

384

  • 416 IntensitiesintheZeemanpattern:weakfields

.

.

.

386

  • 516 ThePaschen-Backeffect

388

  • 616 ThePaschen-Backeffect: illustrativeexamples

.

.

.

390

  • 716 Quadrupolelines

395

CHAPTERXVII

THESTARKEFFECT.

.

.

397

  • 117 Hydrogen

398

  • 217 Starkeffectattheserieslimit

317

417

Generaltheoryfornon-hydrogenicatoms

Helium

517 Alkalimetals

....

404

409

413

415

CHAPTERXVIII

THENUCLEUSINATOMICSPECTRA .

118 Effectoffinitemass

218 418 Localnuclearfields Thehyperfinestructureoftwo-electronspectra

318 Nuclearspininone-electronspectra

.

.

  • 518 Zeemaneffectofhyperfinestructure

.

.

418

418

420

421

424

426

APPENDIX

UNIVERSALCONSTANTSANDNATURAL

ATOMICUNITS

ListofPrincipalTables

IndexofSubjects

....

428

434

435

PREFACE

Inthismonographwehaveundertakenasurveyofthepresentstatusofthe

problemofinterpretingthelinespectraduetoatoms.Thisinterpretation

seemstoustobeinafairlyclosedandhighlysatisfactorystate.Allknown

featuresofatomicspectraarenowatleastsemi-quantitativelyexplained

intermsofthequantum-mechanicaltreatmentofthenuclear-atommodel.

Thisdoesnotmeanthattheperiodoffruitfulresearchinatomicspectra

isatanend.Fundamentalquestionsarestilloutstandinginregardtothe

relativistictheoryofthemany-electronproblemandalsoinregardtothe

theoryoftheinteractionofradiationandmatter.Inadditioneveryreader

willseemanyplaceswheremoreexperimentalinformationandbetteror

thegeneraltypesofcalculationinvolvedandanadequatesurveyofthe moredetailedtheoreticalcalculationsaredesirable.Itisourhopethatthe

bookwillbeusefulinstimulatingprogressalongtheselines.Withthisend

inviewwehaveaimedtogiveexplicitlyanexampleoftheuseofeachof

literatureofthemorespecializedcalculations.Theliteratureiscovered

approximatelytothesummerof1934althoughafewlaterreferences

havebeenincorporated.

Thereexistsconfusionintheoriginalliteratureabouttwomatterswhich

wehavemadeeveryefforttoclearupinthisbook:

Inthefirstplaceithasbeentoolittlerecognizedthatamatrixisnot

fullyusefulinthetransformationtheoryunlesstherelativephasesofthe

statestowhichthecomponentsreferareinsomewayspecified,sincetwo

matricescannotbeaddedormultipliedunlessthesephasesarethesamein

both.Thephasechoiceisarbitrary,justlikethetroublesomesignconven

tionsingeometricaloptics,butonechoicedoeshavetobemadeandadhered

tothroughoutagivensetofcalculations.Tofacilitatetheuseoftheformulas

tomakeexplicitthespecificationofthephasechoiceemployed. andtablesofthebookinothercalculations,wehaveattemptedineverycase

Inthesecondplacethereoccurs,particularlyinthetheoreticalliterature,

agreatdiversityofspectroscopicterminology.Wehaveattemptedto

adhereascloselyaspossibletotheoriginalmeaningsofthenounswhich

denoteenergylevelsandspectrallines,andfindthatthisgivesanomen

claturethatisconvenientandunambiguous. Briefly,ourusageisthe

following :acomponent(ofaline)resultsfromaradiativetransitionbetween

twostatesofanatom;alineresultsfromthetotalityoftransitionsbetween

twolevels; ijxBussell-Saunderscoupling,amultipletisthetotalityoflines

XIV

PREFACE

connectingthelevelsoftwoterms,andasupermultipletisthetotalityof

nmltipletsconnectingthetermsoftwopolyads; atransitionarrayisthe

totalityoflinesconnectingthelevelsoftwoconfigurations.

Wehavedefinedin 74aquantity,calledthestrengthofaline,whichwe

findtogiveamoreconvenienttheoreticalspecificationoftheradiation thisnewusagewillfindfavouramongspectroscopists.

intensitythaneitheroftheEinsteintransitionprobabilities.Wehopethat

Wetakepleasureinmakingacknowledgmenthereofthevaluedhelpof

manyfriendswithwhomwehavediscussedvariouspartsofthetheory,and

whohavecriticizedportionsofthemanuscript.Inparticularwearein

debtedtoProf.BLP.RobertsonofPrincetonformostoftheelegantnew

toMrB.Napierforassistanceinpreparingthefigures.Completionofthe treatmentofsphericalharmonicsgivenin43 ; toDrF.SeitzofPrinceton

andtoProf.C.W.UflfordofAlleghenyCollegeforspecialcalculations;and

workwasgreatlyfacilitatedbygenerousarrangementsbythesenior

authorscolleaguesatPrincetontorelievehimofmostofhisteachingduties

foraterm.Thejuniorauthorisappreciativeofcourtesiesshownbythe

physicsfacultiesoftheUniversityofMinnesota,wherehespentthesummer

of1933,andoftheMassachusettsInstituteofTechnology,wherehespent

theyear1933-1934asaNationalResearchFellow.Thegreaterpartofhis

workonthebookwasdonewhilehewasaFellowinPrincetonUniversity

intheyears1931-1933.

Finallywewishtorecordourgreatenthusiasmforthebeautifultypo

graphicalworkoftheCambridgeUniversityPressasexemplifiedoncemore

inthefollowingpages.

March1935

E.U.C.

G.H.S.

Wearenaturallygratifiedatthereceptionthatourworkhashadandregret

verymuchthatotherdutieshavepreventedourgivingitthethorough 1935editionexceptthatanumberoferrorsandmisprintshavebeen

revisionwhichitneeds.Thepresentprintingisessentiallyareprintofthe

corrected.

May1950

E.U.C.

G.H.S.

CHAPTERI

INTRODUCTION

"AndsothetrueCauseoftheLengthofthatImagewasdetectedtobenoother,

thanthatLightisnotsimilarorHomogenial,butconsistsofDifformRays,some

ofwhicharemoreRefrangiblethanothers." NEWTON.

classicexperimentofNewtonswhich,ledhimtotheconclusionwhichwe Spectroscopyisthatbranchofphysicswhichisthedirectoutgrowthofa

haveplacedattheheadofthischapter.Newtonsexperimentalarrangement

isshowninFig.I1 ,

whichistakenfromVoltairesElemensdelaPhilo-

sophiedeNewton(Amsterdam,1738,p.116).Thebeamofsunlightenters

aholeinthewindowshuttersandtraversestheprism,fallingonthe

screenP.Theimageisnotroundliketheholeintheshutter,butlongin

thedirectionperpendiculartotheaxisoftheprismandcoloured.

Fig.I1 . Newtonsdiscoveryofdispersion.

Thisarrangementistheproto-typeofthemodernspectroscope.Asweare

hereinterestedinthetheoryofspectraweshallnotconcernourselveswith,

thetechniqueofspectroscopyasithasdevelopedfromNewtonstimetothe

present.Ourprincipalinterestwillbetheinformationconcerningthenature

oftheatomwhichisobtainedfromastudyofthecharacteristicradiations

emittedbymonatomicvapours.

Afterthediscoveryofsharpdarklinesinthesolarspectrumandsharp

emissionlinesinspectraofflames,arcs,ardsparks,thephysicistsofthe

nineteenthcenturyseizeduponspectroscopyasavaluabletoolforqualita

tivechemicalanalysis.Atthatstagetheexperimentalproblemconsistedin

correlatingthevariouslinesandbandsseeninthespectroscopewiththe

chemicalnatureoftheemittingsubstance.Thistaskinitselfwasbyno

meanssimple,forthespectroscopeisextraordinarilysensitivetosmall

impuritiesanditwasdifficulttodealwithsourcespureenoughtomake

certainthecorrelationoftheobservedlinestothesubstancesinthesource.

2

INTRODUCTION

Anotherthingwhichmadefordifficultyisthefactthatthespectradonot

dependsimplyonthechemicalelementspresentbutontheirstateof

chemicalcombination,whichinturnisusuallyalteredbytheconditions

whichrenderthesubstanceluminescent.Tothisperiodalsobelongsthe

beginningofthegreattaskofsettingupaccuratestandardsofwave-length.

Itearlybecameclearthattheobservedspectraareofthreegeneraltypes.

Continuous,thatis,havingnolinestructureinthespectroscopesofgreatest

resolvingpower.Theseareemittedbyincandescentsolids,butalsounder somecircumstancesbymoleculesandevenbysingleatoms.Banded,having

aspecialformoflinestructureinwhichclosegroupsofmanylinesoccur

radiationprocess.Line,wherethelinesarewellseparatedandgenerally sodenselypackedthatinsmallerinstrumentstheyappearcontinuous.

Thesearecharacteristicofthespectraofmoleculesandarisefromthe

manypossiblechangesintherotationalstateofthemoleculeduringthe

shownoobvioussimplearrangementalthoughinmanycasestheyare

groupedintosmallrelatedgroupsofafewlines.Suchspectraaredueto

individualatoms.

Thelinespectrumduetoasinglechemicalelementintheformofamon-

atomicvapourshowsstillanothercomplication.Itwasearlylearnedthat

quitedifferentspectraareobtainedfromthesameelementaccordingtothe

energeticviolencewithwhichitisexcitedtoluminescence.Intheelectric

sparkmoreenergyisputintotheemittingatomsthanintheelectricarcand

generallyquitedifferentlinesresultfromthesameelementforthesetwo

modesofexcitation.Thesedifferencesarenowknowntoarisefromdifferent

degreesofionizationofthesameelement.

Evidentlythenextstepisthatoftryingtounderstandthestructural

natureofanatomwhichenablesittoemititscharacteristicradiations.For

thepurposesoftheclassicalkinetictheoryofgasesitisnotnecessaryto

assumeanythingmoreaboutatomsthanthattheybehavesomethinglike

hardelasticballs.Asaconsequencetherangeofphenomenawhichthat

theoryembracesisnotinapositiontotellusmoreaboutthestructureof

atomsthananestimateoftheirsize.Inthespectrumofoneelementweare

givenavastamountofdatawhichismeasurablewithgreatprecision.

Evidentlyitissomehowdeterminedbythestructureoftheatom,so

spectroscopystoodoutclearlyinthemindsofphysicistsasanimportant

meansforstudyingthatstructure.

InthelatterpartofthenineteenthcenturyMaxwelldevelopedhiselectro

magneticwavetheorywhichreceivedexperimentalconfirmationinthe

experimentsofHertzandOliverLodge.Becausethevelocityoflightagreed

withthevelocityofelectricwaves,thetheoryofelectricwaveswasearly

appliedasatheoryoflight.Thewavetheoryoflight,hithertodevelopedas

rNTKODUCTION

o

atheoryofelasticvibrationsintheuniversalmedium,theether,wasre

writtenintermsofthetheoryofelectromagneticwaves.Alittlelaterthe

electronwasdiscoveredthroughresearchesoncathoderaysandthechemical

theoryofionswasdevelopedinconnectionwiththeelectrolyticdissociation

hypothesis.Theviewbecamecurrentthatatomsarestructuresbuiltoutof

electronsandpositiveions.Abranchofphysicscalledtheelectrontheory

ofmattercameintobeingwhoseprogrammecalledfortheexplanationof

thepropertiesofmatterintermsofthispicturewiththeaidofthelawsof

theelectromagneticfield.

Duringthisperiodempiricalregularitiesinlinespectrawerebeingfound.

ThebestknownofthesewasBahnerssimpleformula(1885)forthewave

lengthsofthevisiblelinesofthehydrogenspectrum.

Althoughexperimentalistsstillprefertoexpresstheirmeasurementsin

termsofwave-lengths,Hartleyshowed(1883)thatthereareregularities

inthespacingofrelateddoubletortripletlineswhicharemoresimply

expressedintermsofthereciprocalofthewave-length,thatis,thewave-

numberornumberofwavesinunitlength.Thisdiscoveryisofthegreatest

theoreticalimportance.Thereisnologicalreasonto-dayfordealingwith

wave-lengthsatall,andtheyareseldommentionedinthisbook.Butthe

customofthinkingintermsoftheminthelaboratoryisprobablytoofirmly

entrenchedtobeshakenoffforalongtime.AftertheworkofBalmercomes

theimportantresearchesofRydbergandofKayserandRunge,whodis

coveredthatmanyspectrallinesinvariousatomicspectra,chieflythoseof

alkaliandalkaline-earthmetals,canbeorganizedintoseriesobeying

formulassimilartotheformulaofBalmer.

Theseempiricaldiscoveriesofspectralregularitiesreachtheirculmination

intheclearestablishmentoftheRitzcombinationprinciple.Thiscamein

1908aftertwodecadesofimportantworkonthestudyofspectralseries.

Accordingtothisresulteachatommaybecharacterizedbyasetofnumbers

calledterms,dimensionallylikewave-numbers,suchthattheactualwave-

numbersofthespectrallinesaregivenbydifferencesbetweentheseterms. Ritzthoughtthatlineswereassociatedwithallpossibledifferencesbetween

theseterms,andthisisinaccordwithmoderntheoreticalviews,exceptthat

thelinesassociatedwithsomedifferencesaremillionsoftimesweakerthan whichdifferencesgivestronglines.

otherssothatpracticallythereareimportantselectionrulesneededtotell

Theprinciplereceivedstrikingconfirmationinthesameyearthrough

Paschensdiscoveryofaninfra-redseriesinhydrogen.Thewave-numbers

oftheBalmerseriesarerepresentedbytheformula

4

INTRODUCTION

whereR 109677cm-1 , anempiricalcoefficientcalledtheRydbergcon

stant.InRitzslanguagethismeansthatthisparticularsetoflinesarisesas

differencesofthetermscru=R/7i 2andtheparticulartermcr2=R/2 2 . The

combinationprinciplesuggeststheexistenceoflinesgivenmoregenerallyby

r=R_/1

\m 2

1\

I.

nr]

Form=3and71=4,5,6,...,thelinesfallintheinfra-red.Paschenfound

thematthepredictedplaces*Lymanalsofoundintheultra-violetthreelines asanimportantruleintheanalysisofspectra.Itholdsinallcases,even

correspondingtora=1andn=2,3,4.Theprinciplewasquicklyassimilated

whentheindividualtermscannotberepresentedbyasimpleformulaasis

thecasewithhydrogen.Itsapplicabilityisofgreatgenerality,holdingfor

molecularaswellasatomicspectra.

throughtheworkofPlanckonblack-bodyradiationandEinsteinonthe Thefirstdecadeofthetwentiethcenturywasimportantasshowing,

photo-electriceffect,thatthereismuchmoretothelawsofinteractionof

matterandradiationthanisgivenbythenineteenthcenturyelectromagnetic

theory.Thesedevelopmentsmarkthebirthofquantumtheory.Theelectron

theoryprogrammehadledtosomesimpleassumptionsconcerningatomic

structureandhadhadsomenotablesuccesses,particularlyinLorentzscal

culationoftheeffectofamagneticfieldonthespectrallines,asobservedby

Zeeman.Spectrallineswereassociatedwiththeelectromagneticradiation

comingfrommotionoftheelectronsinanatom,generallyregardedsimply

asharmonicoscillationsaboutanequilibriumposition.Greatdifficulty

attachedtotheinterpretationoftheenormousnumberofspectrallines

withouttheintroductionofunreasonablecomplicationsinthemodel.On

theexperimentalsideamostimportantstepwastherecognition,through

experimentsonscatteringofalphaparticlesmadebyRutherford,thatthe

positiveelectricityinanatomisconfinedtoasmallparticlewhichisnow

calledthenucleusoftheatom.Itslineardimensionsarenotgreaterthan

about10~4thoseofthewholeatom.

ThestageisnowsetforthegreattheoreticaldevelopmentsmadebyBohr

from1913onward.Rutherfordsexperimentshadgivenageneralpicture

ofanuclearatom apositivelychargedmassivenucleussurroundedby

thenegativelychargedandmuchlessmassiveelectrons.Thetheoretical

developmentshadgivenimperfectandunclearindicationsoftheneedof

fundamentalchangesintheelectrontheoryfortheprocessofemissionand

absorptionofradiation.Empiricalspectroscopywasorganizedbymeans

oftheRitzcombinationprincipleandtheextensivestudyofspectralseries.

In1913Bohrsfirstworkonatomicstructuregaveatheoryofthespectrum

ofhydrogenwhichinvolvedseveralimportantadvances.

INTRODUCTION

5

Mostgeneralwastheideaofstationarystatesandtheinterpretationof

theRitzcombinationprinciple.Itispostulatedthatthepossiblestatesof

restrictedtoasetofdiscretevalues.Thenthepostulateismadethatthe atomsandmoleculesarerestrictedtocertainvaluesofthetotalenergy.

Thesevaluesaredeterminedbythestructureoftheatomormoleculeand

maybecontinuousinsomeranges,asintheclassicaltheory,ormaybe

emissionorabsorptionofradiationisconnectedwithaprocessinwhich.

theatompassesfromoneenergyleveltoanother.Thisisrenderedpreciseby

thestatementthatthefrequencyoftheradiationemittedisgivenbythe

wherehisPlanck^sconstant,vthefrequencyoftheradiation,Etheenergy

oftheatombeforetheradiativeprocessandE2itsenergyafterwards.If

E2 > Elthefrequenciescomeoutformallynegative theirnumericalvalues

energyEl arethefrequenciesoflightwhichcanbeabsorbedbyatomsinthestateof . Thisexpressesthefrequenciesasdifferencesofnumberscha

racteristicoftheatomandestablishesacoordinationbetweentheenergy

levels,E,andtheterms,

<r,

throughtherelation

Theminussignarisessincetheconventionalwayofmeasuringtermvalues

wasbycountingthemaspositivewhenmeasuredfrom,theserieslimit.

Thereisnoreasontoadheretothisconvention,sothatweshallalwayswrite

andregardasimplyasameasureoftheenergyintheauxiliaryunit,

1

cm.""

.

Thehypothesissuggestsitsownmeansofexperimentalverification.If

atomsareexcitedtoradiatebysingleelectronimpactsinwhichtheelectrons

haveknownkineticenergyE}thentheonlyspectrallinesappearingshould

bethoseforwhichtheenergyoftheinitialstateE^islessthanE,(This

assumesthatthezeroofenergyistheenergyoftheloweststateandthat

beforeimpacttheatomsareallinthisloweststate.)Thisistheideaunder

lyingtheexperimentsofFranckandHertzandmanyothersoncritical

potentials.Suchexperimentshavefullyconfirmedtheenergylevelinter

pretationofthespectroscopictermsandhavebeenavaluabletoolinexperi

mentalwork.Bycontrolledelectronimpactitispossibletobringouta

spectrumbitbybitasthekineticenergyoftheimpactingelectronsis

graduallyincreased,therebysimplifyingthetaskofdeterminingtheenergy

levelswhichareassociatedwiththeproductionofthedifferentlines.

dynamicalmodelforthehydrogenatomandthestudyofrulesforthe TheotherpartofBohrsearlyworkwasthedevelopmentofaspecial

determinationoftheallowedenergylevels.Themodelforthissimplestatom

consistedofanelectronandprotondescribingorbitsabouttheircentreof

INTRODUCTION

massaccordingtoclassicalmechanicsundertheirmutualattractionasgiven

bytheCoulombinverse-squarelaw.Theallowedcircularorbitswere

determinedsimplybytherequirement(anadditionalpostulateofthe

quantumtheory)thattheangularmomentumofthesystembeanintegral

multipleofH=hjSir.Thisservedtogiveanenergy

^=-

forthecircularorbitwhoseangularmomentumisnti,whencetheterm

n^ he nextfewyearsgseatadvancesweremadeininterpretationoffinerdetailsof

vakesare

Notonlyisthevariationas?r~2inaccordwiththeschemeoftermsasgiven

bytheLyman-Balmer-Paschenseriesinhydrogen,butthenumerical

coefficientcomesoutcorrectly,sobythismeanstheempiricalEydberg

constantRwasforthefirsttimerelatedtouniversalconstants.

Naturallythisdefiniteaccomplishmentstimulatedotherworkandinthe

thehydrogenspectrumduetorelativisticeffects(Sommerfeld)andtheeffect

ofanelectricfieldonthehydrogenspectrum(Epstein,Schwarzschild).Also

itgaverisetomuchImportantworkinextendingthemodelandthequantum

principletoothermorecomplicatedatomicandmolecularstructures.These

studieswereeminentlysuccessfulinasemi-quantitativewayandgaveagreat

impetustotheexperimentalstudyandanalysisofatomicspectra.Thetheory

calledforastudyofthemodelbymeansofclassicalmechanics.Theso-

calledmultiplyperiodicmotionshadtobesoughtoutandofthesethe

allowedonesdeterminedbyaruleofquantizationwhichwasanoutgrowth

ofBohrsrequirementontheangularmomentumforthecircularorbitsof

hydrogen.Weshallnottraceindetailtheworkalongtheselines:forthis

thereaderisreferredtoSommerfeldsAtombauundSpeJctrallinienandto

VanVlecksQuantumPrinciplesandLineSpectra.

interactionoftheatomwiththeelectromagneticfield.Itgavenodefinite Thetheorywasquiteincomplete,however,inregardtothedetailsofthe

basisforthecalculationoftherelativeorabsoluteintensitiesofthespectral

lines.Italsofailedtogivesatisfactoryresultswhenattemptsweremadeto

calculatetheenergylevelsofatomscontainingmorethanoneelectron.

Numerousattemptsweremadetocalculatetheenergyoftheloweststateof

heliumbutwithoutsecuringagreementwiththeexperimentalresult.

EvidentlyBohrsprincipleshadtoberegardedasprovisionalindications

ofthedirectioninwhichamoresatisfactorytheorywastobesought.The

unsatisfactorinessofthetheorycamemoreandmoreintotheforeground

intheearlypartofthe1920-30decadeafteralmosttenyearsinwhich

INTRODUCTION"

7

physicistswerebusymakingsuchprogressaswaspossiblewiththeoriginal

Bohrtheory.

Thiswastheperiodjustprecedingthediscoveryoftheformalismof

quantummechanics,thediscoverywhichhasbeensoextraordinarily

fruitfulforallpartsofatomicphysicsinthepasteightyears.Inthisperiod

muchwasdoneinthestudyofatomic