Quantum Control of Molecular Processes, Second Edition

551 Pages·2011·14.088 MB·English

by  Prof. Moshe Shapiro, Prof. Paul Brumer(auth.)

MosheShapiroandPaulBrumer
QuantumControlofMolecular
Processes
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Moshe Shapiro and Paul Brumer
Quantum Control of Molecular Processes
Second, Revised and Enlarged Edition
WILEY-VCH Verlag GmbH & Co. KGaA
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Inmemoryofourparentsand
toourwivesRachelleandAbbey,(cid:2)ל(cid:2)י(cid:2)ח(cid:2)י(cid:2)ש(cid:2)נ
VII
Contents
PrefacetotheSecondEdition XIII
PrefacetotheFirstEdition XV
1 PreliminariesoftheInteractionofLightwithMatter 1
2 Weak-FieldPhotodissociation 5
2.1 PhotoexcitationofaMoleculewithaPulseofLight 6
2.2 StatePreparationDuringthePulse 8
2.3 Photodissociation 13
2.3.1 GeneralFormalism 13
2.3.2 ElectronicStates 20
2.3.3 Energy-ResolvedQuantities 21
2.A Appendix:MolecularStateLifetimeinPhotodissociation 22
3 Weak-FieldCoherentControl 25
3.1 TraditionalExcitation 25
3.2 PhotodissociationfromaSuperpositionState 26
3.2.1 BichromaticControl 28
3.2.2 EnergyAveragingandSatelliteContributions 31
3.3 ThePrincipleofCoherentControl 33
3.4 InterferencebetweenN-PhotonandM-PhotonRoutes 35
3.4.1 MultiphotonAbsorption 35
3.4.2 One-vs.Three-PhotonInterference 39
3.4.2.1 One-vs.Three-PhotonInterference:Three-Dimensional
Formalism 41
3.4.3 One-vs.Two-PhotonInterference:SymmetryBreaking 50
3.5 PolarizationControlofDifferentialCrossSections 56
3.6 Pump-DumpControl:FewLevelExcitation 57
3.A Appendix:Mode-SelectiveChemistry 68
4 ControlofIntramolecularDynamics 71
4.1 IntramolecularDynamics 71
4.1.1 TimeEvolutionandtheZero-OrderBasis 72
4.1.2 PartitioningoftheHilbertSpace 73
VIII Contents
4.1.3 InitialStateControlandOverlappingResonances 75
4.1.3.1 InternalConversioninPyrazine 77
4.1.3.2 IntramolecularVibrationalRedistribution:OCS 78
5 OptimalControlTheory 83
5.1 Pump-Dump Excitation with Many Levels: the Tannor–Rice
Scheme 83
5.2 OptimalControlTheory 89
5.2.1 GeneralPrinciplesofOptimalControlTheory 89
6 DecoherenceandItsEffectsonControl 95
6.1 Decoherence 95
6.1.1 MasterEquations 98
6.2 SampleComputationalResultsonDecoherence 100
6.2.1 ElectronicDecoherence 100
6.2.2 VibrationalDecoherenceinCondensedPhases 102
6.2.3 Decoherence:TowardstheClassicalLimit 106
6.3 EnvironmentalEffectsonControl:SomeTheorems 109
6.3.1 EnvironmentCanLimitControl 109
6.3.2 EnvironmentCanEnhanceControl 112
6.3.2.1 EnvironmentallyAssistedTransport 112
6.3.3 EnvironmentallyAssistedOne-PhotonPhaseControl 114
6.3.4 IsolatedMolecules 116
6.3.5 NonisolatedSystems 117
6.4 DecoherenceandControl 119
6.4.1 TheOpticalBlochEquation 120
6.4.1.1 DecoherenceEffectsinOne-Photonvs.Three-Photon
Absorption 121
6.4.2 CounteringCollisionalEffects 126
6.4.3 AdditionalControlStudies 129
6.4.4 StateStabilityagainstDecoherence 133
6.4.5 OverlappingResonancesandDecoherenceControl:Qualitative
Motivation 135
6.4.6 ControlofDephasing 139
6.5 Countering Partially Coherent Laser Effects in Pump-Dump
Control 142
6.6 CounteringCWLaserJitter 149
6.6.1 LaserPhaseAdditivity 150
6.6.2 IncoherentInterferenceControl 151
7 CaseStudiesinCoherentControl 153
7.1 Two-Photonvs.Two-PhotonControl 153
7.1.1 ExperimentalImplementation 160
7.2 ControlovertheRefractiveIndex 169
7.2.1 BichromaticControl 171
7.3 TheMolecularPhaseinthePresenceofResonances 176
Contents IX
7.3.1 TheoryofScatteringResonances 178
7.3.2 Three-Photonvs.One-PhotonCoherentControlinthePresence
ofResonances 182
7.3.2.1 Case (a): an Indirect Transition to an Isolated
Resonance 184
7.3.2.2 Case (b): a Purely Direct Transition to the
Continuum 184
7.3.2.3 Case(c):anIndirectTransitiontoaSetofOverlapping
Resonances 185
7.3.2.4 Case(d):aSumofDirectandIndirectTransitiontoan
IsolatedResonance 185
7.4 ControlofChaoticDynamics 186
8 CoherentControlofBimolecularProcesses 191
8.1 FixedEnergyScattering:EntangledInitialStates 191
8.1.1 IssuesinthePreparationoftheScatteringSuperposition 193
8.1.2 IdenticalParticleCollisions 195
8.1.3 SampleControlResults 198
8.1.3.1 mSuperpositions 198
8.1.3.2 Control in Cold Atoms: Penning vs. Dissociative
Ionization 201
8.1.3.3 ControlinElectronImpactDissociation 207
8.1.4 ExperimentalImplementation:FixedTotalEnergy 211
8.1.5 OptimalControlofBimolecularScattering 212
8.1.5.1 Optimized Bimolecular Scattering: the Total
SuppressionofaReactiveEvent 214
8.1.6 SculptedImplodingWaves 216
8.2 TimeDomain:FastTimedCollisions 217
8.2.1 NonentangledWavePacketSuperpositions:Time-Dependent
Scattering 217
8.2.2 EntangledorWavePackets? 220
9 TheInteractionofLightwithMatter:aCloserLook 223
9.1 ClassicalElectrodynamicsofaPulseofLight 223
9.1.1 TheClassicalHamiltonian 223
9.1.2 TheFreeLightField 226
9.2 TheDynamicsofQuantizedParticlesandClassicalLightFields 228
10 CoherentControlwithQuantumLight 233
10.1 TheQuantizationoftheElectromagneticField 233
10.1.1 Light–MatterInteractions 235
10.2 QuantumLightandQuantumInterference 236
10.2.1 One-Photonvs.Two-PhotonQuantumFieldControl 238
10.2.1.1UseofNumberStates 238
10.2.1.2UseofCoherentStates 239
10.2.2 Pump-DumpCoherentControl 240
X Contents
10.2.2.1ResultswithQuantizedLight 240
10.2.2.2ResultswithClassicalFields 242
10.2.3 Phase-IndependentControl 243
10.3 QuantumFieldControlofEntanglement 245
10.3.1 Light–MatterEntanglement 245
10.3.2 CreatingEntanglementbetween aChainofMoleculesanda
RadiationField 247
10.4 ControlofEntanglementinQuantumFieldChiralSeparation 250
11 Coherent Control beyond the Weak-Field Regime: Bound States and
Resonances 253
11.1 AdiabaticPopulationTransfer 253
11.1.1 AdiabaticStates,Trapping,andAdiabaticFollowing 254
11.1.2 TheMultistateExtensionofSTIRAP 260
11.2 An Analytic Solution of the Nondegenerate Quantum Control
Problem 261
11.3 TheDegenerateQuantumControlProblem 266
11.4 AdiabaticEncodingandDecodingofQuantumInformation 271
11.5 MultistatePiecewiseAdiabaticPassage 275
11.5.1 MultistatePiecewiseAdiabaticPassage–Experiments 280
11.5.1.1ChirpedAdiabaticPassage 281
11.5.1.2RabiFlopping 283
11.6 ElectromagneticallyInducedTransparency 290
11.6.1 EIT:aResonancePerspective 291
11.6.2 EIT as Emerging from the Interference between
Resonances 293
11.6.2.1UnstructuredContinua 300
11.6.2.2StructuredContinua 300
11.6.3 Photoabsorption 301
11.6.4 The Resonance Description of Slowing Down of Light by
EIT 306
12 PhotodissociationBeyondtheWeak-FieldRegime 315
12.1 One-PhotonDissociationwithLaserPulses 315
12.1.1 SlowlyVaryingContinuum 318
12.1.2 BichromaticControl 319
12.1.3 Resonance 319
12.2 ComputationalExamples 325
13 CoherentControlBeyondtheWeak-FieldRegime:theContinuum 329
13.1 ControloverPopulationTransfer totheContinuumbyTwo-Photon
Processes 329
13.1.1 The Adiabatic Approximation for a Final Continuum
Manifold 330
13.2 PulsedIncoherentInterferenceControl 335
13.3 ResonantlyEnhancedPhotoassociation 345
Contents XI
13.3.1 TheoryofPhotoassociationofaCoherentWavePacket 346
13.3.2 PhotoassociationbytheConsecutiveApplicationofAPCand
STIRAP 353
13.3.3 InterferencebetweenDifferentPathways 357
13.3.4 ExperimentalRealizations 359
13.4 LaserCatalysis 363
13.4.1 TheCouplingofaBoundStateto TwoContinuabyaLaser
Pulse 364
14 CoherentControloftheSynthesisandPurificationofChiralMolecules 373
14.1 PrinciplesofElectricDipoleAllowedEnantiomericControl 374
14.2 Symmetry Breaking in the Two-Photon Dissociation of Pure
States 376
14.3 PurificationofRacemicMixturesby“LaserDistillation” 381
14.4 EnantiomerControl:OrientedMolecules 395
14.5 AdiabaticPurificationofMixturesofRight-HandedandLeft-Handed
ChiralMolecules 397
14.5.1 VibrationalStateDiscriminationofChiralMolecules 399
14.5.2 SpatialSeparationofEnantiomers 404
14.5.3 InternalHamiltonianandDressedStates 405
14.5.4 LaserConfiguration 408
14.5.5 SpatialSeparationUsingaColdMolecularTrap 409
14.A Appendix:ComputationofB(cid:2)A(cid:2)B0EnantiomerSelectivity 413
15 Strong-FieldCoherentControl 415
15.1 Strong-Field Photodissociationwith ContinuousWave Quantized
Fields 415
15.1.1 TheCoupled-ChannelsExpansion 419
15.1.2 NumberStatesvs.ClassicalLight 423
15.2 Strong-FieldPhotodissociationwithPulsedQuantizedFields 425
15.2.1 Light-InducedPotentials 426
15.3 ControlledFocusing,Deposition,andAlignmentofMolecules 429
15.3.1 FocusingandDeposition 429
15.3.2 Strong-FieldMolecularAlignment 435
16 CoherentControlwithFew-CyclePulses 443
16.1 TheCarrierEnvelopePhase 443
16.2 CoherentControlandtheCEOFrequencyMeasurement 445
16.3 TheRecollisionModel 446
16.3.1 Step1:TunnelIonization 447
16.3.2 Step2:Classical“Swing”Motion 448
16.3.3 Step3:Recollision 448
16.3.4 Step4:EmissionofaPhoton 450
16.4 CEPStabilizationandControl 451
16.4.1 TheAttosecondStreakCamera 452
16.5 CoherentControlofSampleMolecularSystems 453