Molecules in electromagnetic fields: from ultracold physics to controlled chemistry

387 Pages·2019·5.339 MB·English

by  Krems, Roman V

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MoleculesinElectromagneticFields
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Molecules in Electromagnetic Fields
FromUltracoldPhysicstoControlledChemistry
RomanV.Krems
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Thiseditionfirstpublishedcopyrightyear2019
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LibraryofCongressCataloging-in-PublicationData
Names:Krems,RomanV.,1977-author.
Title:Moleculesinelectromagneticfields:fromultracoldphysicsto
controlledchemistry/byRomanV.Krems.
Description:1stedition.|Hoboken,NJ:JohnWiley&Sons,2019.|Includes
index.|
Identifiers:LCCN2017053373(print)|LCCN2017060297(ebook)|ISBN
9781119387350(pdf)|ISBN9781119387398(epub)|ISBN9781118173619
(cloth)
Subjects:LCSH:Molecules.|Electromagneticfields.
Classification:LCCQC173.3(ebook)|LCCQC173.3.K742019(print)|DDC
539/.6–dc23
LCrecordavailableathttps://lccn.loc.gov/2017053373
CoverdesignbyWiley
Coverimage:©RomanKrems
Setin10/12ptWarnockbySPiGlobal,Chennai,India
PrintedintheUnitedStatesofAmerica
10987654321
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ContentsinBrief
1 IntroductiontoRotational,Fine,andHyperfineStructureof
MolecularRadicals 1
2 DCStarkEffect 35
3 ZeemanEffect 59
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5 MolecularRotationsUnderControl 121
6 ExternalFieldTraps 145
7 MoleculesinSuperimposedFields 175
8 MolecularCollisionsinExternalFields 187
9 MatrixElementsofCollisionHamiltonians 217
10 Field-InducedScatteringResonances 239
11 FieldControlofMolecularCollisions 257
12 UltracoldControlledChemistry 283
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Contents
ListofFigures xiii
ListofTables xxv
Preface xxvii
Acknowledgments xxxi
1 IntroductiontoRotational,Fine,andHyperfineStructureof
MolecularRadicals 1
1.1 WhyMoleculesareComplex 1
(cid:2) 1.2 SeparationofScales 3 (cid:2)
1.2.1 ElectronicEnergy 5
1.2.2 VibrationalEnergy 10
1.2.3 RotationalandFineStructure 14
1.3 RotationofaMolecule 17
1.4 Hund’sCases 21
1.4.1 Hund’sCouplingCase(a) 21
1.4.2 Hund’sCouplingCase(b) 22
1.4.3 Hund’sCouplingCase(c) 23
1.5 ParityofMolecularStates 23
1.6 GeneralNotationforMolecularStates 27
1.7 HyperfineStructureofMolecules 28
1.7.1 MagneticInteractionswithNuclei 28
1.7.2 FermiContactInteraction 29
1.7.3 Long-RangeMagneticDipoleInteraction 30
1.7.4 ElectricQuadrupoleHyperfineInteraction 31
Exercises 31
2 DCStarkEffect 35
2.1 ElectricFieldPerturbations 35
2.2 ElectricDipoleMoment 37
2.3 LinearandQuadraticStarkShifts 40
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viii Contents
2.4 StarkShiftsofRotationalLevels 42
2.4.1 Moleculesina1ΣElectronicState 42
2.4.2 Moleculesina2ΣElectronicState 46
2.4.3 Moleculesina3ΣElectronicState 48
2.4.4 Moleculesina1ΠElectronicState–Λ-Doubling 51
2.4.5 Moleculesina2ΠElectronicState 54
Exercises 56
3 ZeemanEffect 59
3.1 TheElectronSpin 59
3.1.1 TheDiracEquation 60
3.2 ZeemanEnergyofaMovingElectron 63
3.3 MagneticDipoleMoment 64
3.4 ZeemanOperatorintheMolecule-FixedFrame 66
3.5 ZeemanShiftsofRotationalLevels 67
3.5.1 Moleculesina2ΣState 67
3.5.2 Moleculesina2ΠElectronicState 71
3.5.3 IsolatedΣStates 74
3.6 NuclearZeemanEffect 75
3.6.1 ZeemanEffectina1ΣMolecule 76
(cid:2) Exercises 78 (cid:2)
4 ACStarkEffect 81
4.1 PeriodicHamiltonians 82
4.2 TheFloquetTheory 84
4.2.1 FloquetMatrix 88
4.2.2 TimeEvolutionOperator 89
4.2.3 BriefSummaryofFloquetTheoryResults 90
4.3 Two-ModeFloquetTheory 92
4.4 RotatingWaveApproximation 94
4.5 DynamicDipolePolarizability 96
4.5.1 PolarizabilityTensor 97
4.5.2 DipolePolarizabilityofaDiatomicMolecule 99
4.5.3 RotationalvsVibrationalvsElectronicPolarizability 101
4.6 MoleculesinanOff-ResonantLaserField 104
4.7 MoleculesinaMicrowaveField 107
4.8 MoleculesinaQuantizedField 109
4.8.1 FieldQuantization 109
4.8.2 InteractionofMoleculeswithQuantizedField 116
4.8.3 QuantizedFieldvsFloquetTheory 117
Exercises 118
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