Table of Contents
Preface v
1 Theoretical Foundations for Exploring Quantum Optimal Control of Molecules Tak-San Ho Herschel Rabitz Shih-I Chu 1
1 Introduction 2
2 Time-dependent Molecular Dynamics Equations 6
3 Quantum OCT for the State-to-State Transition Probability: The Lagrange Multipliers Method 7
4 Theory of QCL for the State-to-State Transition Probability 11
4.1 Kinematic critical points 12
4.2 Quantum control landscape 13
5 A TBQCP for State-to-State Transition Probability Control 16
6 Optimal Control in the Weak Field Limit: The Adiabatic NBO Representation 20
7 Optimal Control in the Strong Field Limit - The Adiabatic ENBO Representation 26
8 Optimal Control in the Adiabatic TDBO Representation 32
9 Monotonically Convergent Optimal Control Search Algorithms: TBQCP Method 38
10 Applications of the Monotonically Convergent TBQCP Method 41
10.1 Molecular photoassociation along with vibrational stabilization 41
10.2 Selective bond breakage in gas-phase dihaiomethanes CH2BrCl 41
10.3 Field-free orientation of a OCS thermal ensemble 43
10.4 Vibrational excitation of H2 molecules 46
11 Summary 49
Acknowledgments 49
Appendix: Alternating Forward/Backward Control Field Updating 50
Reference 54
2 Intramolecular Nuclear Flux Densities I. Barth C. Daniel E. Gindensperger J. Manz J. F. Pérez-Torres A. Schild C. Stemmle D. Sulzer Y. Yang 59
1 Introduction 60
2 Methods, Results and Discussions 62
2.1 Experimental results for nuclear flux densities in vibrating Na2 and D+2, deduced from pump-probe spectra 62
2.2 Quantum model simulations of the nuclear flux densities in vibrating I2 and H+269
2.3 Nuclear flux densities in ID model systems with symmetric double-well potentials 78
2.4 Nuclear flux density and induced magnetic field in pseudorotating OSH4 and ReH-4 87
3 Conclusions 103
Acknowledgments 105
Reference 105
3 Femtosecond Structural Study of Reacting Excited-State Molecules Through Observation of Nuclear Wavepacket Motions Satoshi Takeuchi Tahei Tahara 111
1 Introduction 111
2 Nuclear Wavepacket Motions in the Excited State as Observed by Pumb-Probc Measurements 114
2.1 Generation and observation of nuclear wavepacket motions 115
2.2 Selection rules 118
2.3 Setup for ultrafast two-color pump-probe spectroscopy 120
2.4 Example: Si trans-stilbene 123
2.4.1 Time-domain signal and its comparison with frequency-domain data 123
2.4.2 Quantitative estimation of relative band intensities 126
3 Initial Nuclear Wavepacket Motions of Reacting Excited-state Molecules as Observed by Pump-Probe Spectroscopy 131
3.1 Photoisomerization of cis-stilbene 131
3.2 Photodissociation of diphenylcyclopropenone 135
3.3 Intramolecular proton transfer of 10-hydroxybenzoquinoline 140
4 Structural Tracking by Time-resolved Impulsive Raman 146
4.1 Time-resolved impulsive stimulated Raman spectroscopy 147
4.2 Setup for TR-ISRS experiment 149
4.3 TR-ISRS studies of photoisomerization of cis-stilbene 151
4.3.1 TR-ISRS measurements 151
4.3.2 Comparison with theoretical calculations 156
4.4 Conceptual advance: Observation of continuous structural change 159
5 Concluding Remarks and Outlook 159
Acknowledgments 160
Reference 160
4 Study of Water Interfaces with Phase-Sensitive Sum Frequency Vibrational Spectroscopy Chuanshan Tian 163
1 Introduction 163
2 Basics of SFVS 166
2.1 General description of SFVS 166
2.2 Phase-sensitive sum frequency vibrational spectroscopy 169
3 Application of SFVS for Water Interfaces 171
3.1 Studies of neat water/air interfaces 171
3.2 Studies of ion adsorption at water/air interfaces 178
3.3 Studies of water/hydrophobic interfaces 182
3.4 Studies of water/oxide interfaces 186
4 Conclusions 188
Reference 189
5 Magneto-Chiral Dichroism of Organic Compounds Yuichi Kitagawa Kazuyuki Ishii 195
1 Introduction 195
2 General Theory of MchD 197
3 MChD of Metal Compounds 200
3.1 Observations of MChD for metal compounds 200
3.2 Enantiosetectivc reactions based on the MChD of metal complexes 203
4 MChD of Aromatic π-Conjugated Systems 205
4.1 MChD of organic compounds 205
4.2 MChD of light-harvesting antenna 209
5 Theoretical Explanations for MChD Based on Exciton Chirality 212
6 Conclusions and Future Directions 214
Reference 214
Appendix 217
Index 259
