Quantum Control of Molecular Processes

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Spis treści:
Preface to the Second Edition XIII
Preface to the First Edition XV
1 Preliminaries of the Interaction of Light with Matter 1
2 Weak–Field Photodissociation 5
2.1 Photoexcitation of a Molecule with a Pulse of Light 6
2.2 State Preparation During the Pulse 8
2.3 Photodissociation 13
2.3.1 General Formalism 13
2.3.2 Electronic States 20
2.3.3 Energy–Resolved Quantities 21
2.A Appendix: Molecular State Lifetime in Photodissociation 22
3 Weak–Field Coherent Control 25
3.1 Traditional Excitation 25
3.2 Photodissociation from a Superposition State 26
3.2.1 Bichromatic Control 28
3.2.2 Energy Averaging and Satellite Contributions 31
3.3 The Principle of Coherent Control 33
3.4 Interference between N–Photon and M–Photon Routes 35
3.4.1 Multiphoton Absorption 35
3.4.2 One– vs. Three–Photon Interference 39
3.4.2.1 One– vs. Three–Photon Interference: Three–Dimensional Formalism 41
3.4.3 One– vs. Two–Photon Interference: Symmetry Breaking 50
3.5 Polarization Control of Differential Cross Sections 56
3.6 Pump–Dump Control: Few Level Excitation 57
3.A Appendix: Mode–Selective Chemistry 68
4 Control of Intramolecular Dynamics 71
4.1 Intramolecular Dynamics 71
4.1.1 Time Evolution and the Zero–Order Basis 72
4.1.2 Partitioning of the Hilbert Space 73
4.1.3 Initial State Control and Overlapping Resonances 75
4.1.3.1 Internal Conversion in Pyrazine 77
4.1.3.2 Intramolecular Vibrational Redistribution: OCS 78
5 Optimal Control Theory 83
5.1 Pump–Dump Excitation w ith Many Levels: the Tannor–Rice Scheme 83
5.2 Optimal Control Theory 89
5.2.1 General Principles of Optimal Control Theory 89
6 Decoherence and Its Effects on Control 95
6.1 Decoherence 95
6.1.1 Master Equations 98
6.2 Sample Computational Results on Decoherence 100
6.2.1 Electronic Decoherence 100
6.2.2 Vibrational Decoherence in Condensed Phases 102
6.2.3 Decoherence: Towards the Classical Limit 106
6.3 Environmental Effects on Control: Some Theorems 109
6.3.1 Environment Can Limit Control 109
6.3.2 Environment Can Enhance Control 112
6.3.2.1 Environmentally Assisted Transport 112
6.3.3 Environmentally Assisted One–Photon Phase Control 114
6.3.4 Isolated Molecules 116
6.3.5 Nonisolated Systems 117
6.4 Decoherence and Control 119
6.4.1 The Optical Bloch Equation 120
6.4.1.1 Decoherence Effects in One–Photon vs. Three–Photon Absorption 121
6.4.2 Countering Collisional Effects 126
6.4.3 Additional Control Studies 129
6.4.4 State Stability against Decoherence 133
6.4.5 Overlapping Resonances and Decoherence Control: Qualitative Motivation 135
6.4.6 Control of Dephasing 139
6.5 Countering Partially Coherent Laser Effects in Pump–Dump Control 142
6.6 Countering CW Laser Jitter 149
6.6.1 Laser Phase Additivity 150
6.6.2 Incoherent Interference Control 151
7 Case Studies in Coherent Control 153
7.1 Two–Photon vs. Two–Photon Control 153
7.1.1 Experimental Implementation 160
7.2 Control over the Refractive Index 169
7.2.1 Bichromatic Control 171
7.3 The Molecular Phase in the Presence of Resonances 176
7.3.1 Theory of Scattering Resonances 178
7.3.2 Three–Ph oton vs. One–Photon Coherent Control in the Presence of Resonances 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): an Indirect Transition to a Set of Overlapping Resonances 185
7.3.2.4 Case (d): a Sum of Direct and Indirect Transition to an Isolated Resonance 185
7.4 Control of Chaotic Dynamics 186
8 Coherent Control of Bimolecular Processes 191
8.1 Fixed Energy Scattering: Entangled Initial States 191
8.1.1 Issues in the Preparation of the Scattering Superposition 193
8.1.2 Identical Particle Collisions 195
8.1.3 Sample Control Results 198
8.1.3.1 m Superpositions 198
8.1.3.2 Control in Cold Atoms: Penning vs. Dissociative Ionization 201
8.1.3.3 Control in Electron Impact Dissociation 207
8.1.4 Experimental Implementation: Fixed Total Energy 211
8.1.5 Optimal Control of Bimolecular Scattering 212
8.1.5.1 Optimized Bimolecular Scattering: the Total Suppression of a Reactive Event 214
8.1.6 Sculpted ImplodingWaves 216
8.2 Time Domain: Fast Timed Collisions 217
8.2.1 Nonentangled Wave Packet Superpositions: Time–Dependent Scattering 217
8.2.2 Entangled or Wave Packets? 220
9 The Interaction of Light with Matter: a Closer Look 223
9.1 Classical Electrodynamics of a Pulse of Light 223
9.1.1 The Classical Hamiltonian 223
9.1.2 The Free Light Field 226
9.2 The Dynamics of Quantized Particles and Classical Light Fields 228
10 Coherent Control with Quantum Light 233
10.1 The Quantization of the Electromagnetic Field 233
10.1.1 Light–Matter Interactions 235
10.2 Quantum Light and Quantum Interference 236
10.2.1 One–Photo n vs. Two–Photon Quantum Field Control 238
10.2.1.1 Use of Number States 238
10.2.1.2 Use of Coherent States 239
10.2.2 Pump–Dump Coherent Control 240
10.2.2.1 Results with Quantized Light 240
10.2.2.2 Results with Classical Fields 242
10.2.3 Phase–Independent Control 243
10.3 Quantum Field Control of Entanglement 245
10.3.1 Light–Matter Entanglement 245
10.3.2 Creating Entanglement between a Chain of Molecules and a Radiation Field 247
10.4 Control of Entanglement in Quantum Field Chiral Separation 250
11 Coherent Control beyond the Weak–Field Regime: Bound States and Resonances 253
11.1 Adiabatic Population Transfer 253
11.1.1 Adiabatic States, Trapping, and Adiabatic Following 254
11.1.2 The Multistate Extension of STIRAP 260
11.2 An Analytic Solution of the Nondegenerate Quantum Control Problem 261
11.3 The Degenerate Quantum Control Problem 266
11.4 Adiabatic Encoding and Decoding of Quantum Information 271
11.5 Multistate Piecewise Adiabatic Passage 275
11.5.1 Multistate Piecewise Adiabatic Passage – Experiments 280
11.5.1.1 Chirped Adiabatic Passage 281
11.5.1.2 Rabi Flopping 283
11.6 Electromagnetically Induced Transparency 290
11.6.1 EIT: a Resonance Perspective 291
11.6.2 EIT as Emerging from the Interference between Resonances 293
11.6.2.1 Unstructured Continua 300
11.6.2.2 Structured Continua 300
11.6.3 Photoabsorption 301
11.6.4 The Resonance Description of Slowing Down of Light by EIT 306
12 Photodissociation Beyond the Weak–Field Regime 315
12.1 One–Photon Dissociation with Laser Pulses 315
12.1.1 Slowly Varying Continuum 318
12.1.2 Bichromatic Control 319
12.1.3 Re sonance 319
12.2 Computational Examples 325
13 Coherent Control Beyond the Weak–Field Regime: the Continuum 329
13.1 Control over Population Transfer to the Continuum by Two–Photon Processes 329
13.1.1 The Adiabatic Approximation for a Final Continuum Manifold 330
13.2 Pulsed Incoherent Interference Control 335
13.3 Resonantly Enhanced Photoassociation 345
13.3.1 Theory of Photoassociation of a Coherent Wave Packet 346
13.3.2 Photoassociation by the Consecutive Application of APC and STIRAP 353
13.3.3 Interference between Different Pathways 357
13.3.4 Experimental Realizations 359
13.4 Laser Catalysis 363
13.4.1 The Coupling of a Bound State to Two Continua by a Laser Pulse 364
14 Coherent Control of the Synthesis and Purification of Chiral Molecules 373
14.1 Principles of Electric Dipole Allowed Enantiomeric Control 374
14.2 Symmetry Breaking in the Two–Photon Dissociation of Pure States 376
14.3 Purification of Racemic Mixtures by “Laser Distillation” 381
14.4 Enantiomer Control: Oriented Molecules 395
14.5 Adiabatic Purification of Mixtures of Right–Handed and Left–Handed Chiral Molecules 397
14.5.1 Vibrational State Discrimination of Chiral Molecules 399
14.5.2 Spatial Separation of Enantiomers 404
14.5.3 Internal Hamiltonian and Dressed States 405
14.5.4 Laser Configuration 408
14.5.5 Spatial Separation Using a Cold Molecular Trap 409
14.A Appendix: Computation of BAB0 Enantiomer Selectivity 413
15 Strong–Field Coherent Control 415
15.1 Strong–Field Photodissociation with Continuous Wave Quantized Fields 415
15.1.1 The Coupled–Channels Expansion 419
15.1.2 Number States vs. Classical Light 423
15.2 Strong–Field Photodissociation with Pulsed Quantized Fields 425
15.2.1 Light–Induced Potentials 426
15.3 Controlled Focusing, Deposition, and Alignment of Molecules 429
15.3.1 Focusing and Deposition 429
15.3.2 Strong–Field Molecular Alignment 435
16 Coherent Control with Few–Cycle Pulses 443
16.1 The Carrier Envelope Phase 443
16.2 Coherent Control and the CEO Frequency Measurement 445
16.3 The Recollision Model 446
16.3.1 Step 1: Tunnel Ionization 447
16.3.2 Step 2: Classical “Swing” Motion 448
16.3.3 Step 3: Recollision 448
16.3.4 Step 4: Emission of a Photon 450
16.4 CEP Stabilization and Control 451
16.4.1 The Attosecond Streak Camera 452
16.5 Coherent Control of Sample Molecular Systems 453
16.5.1 One–Photon vs. Two–Photon Control with Few–Cycle Pulses 453
16.5.1.1 Backward–Forward Asymmetry in the Dissociative Photoionization of D2. 453
16.5.2 Control of the Generation of High–Harmonics 455
16.5.3 Control of Electron Transfer Processes 456
16.5.4 Electron Transfer in Alkali Halides 457
17 Case Studies in Optimal Control 463
17.1 Creating Excited States 463
17.1.1 Using Prepared States 467
17.2 Optimal Control in the Perturbative Domain 468
17.3 Adaptive Feedback Control 471
17.4 Analysis of Adaptive Feedback Experiments 480
17.4.1 trans–cis Isomerization in 3,30–Diethyl–2,20–thiacyanine Iodide 480
17.4.2 Controlled Stokes Emission vs. Vibrational Excitation in Methanol 486
17.5 Interference and Optimal Control 487
18 Coherent Control in the Classical Limit 491
18.1 The One–Photon vs. Two–Photon Scenario Revisited 491
18.1.1 Resonant Regime 491
18.1.2 Off–Resonant Extension 492
18.1.3 A Three–State Example 494
18.1.4 Quantum Features 495
18.2 The Quartic Oscillator 496
18.3 Control in an Optical Lattice 499
18.3.1 Equivalence with Dipole Driving 501
18.3.2 Computational Results 502
Appendix Common Notation Used in the Book (in Order of Appearance) 507
References 513
Subject Index 537

Nota biograficzna:
Moshe Shapiro is a Canada Research Chair Professor on Quantum Control at the Department of Chemistry, the University of British Columbia, Vancouver, Canada. He received his BSc, MSc, and PhD from the Hebrew University of Jerusalem.
Paul Brumer is University Professor of Chemistry and holds the Roel Buck Chair in Chemical Physics at the University of Toronto. He received his BSc from Brooklyn College and his PhD from Harvard University. The authors are among the cofounders of the field of coherent control. They have published extensively on this and related subjects in chemical physics, and have received numerous awards and worldwide recognition for their research contributions.

Okładka tylna:
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