Quantum Control of Molecular Processes E-Book

Moshe Shapiro

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 930

Veröffentlichungsjahr: 2012

Beschreibung

Written by two of the world's leading researchers in the field, this is a systematic introduction to the fundamental principles of coherent control, and to the underlying physics and chemistry.

This fully updated second edition is enhanced by 80% and covers the latest techniques and applications, including nanostructures, attosecond processes, optical control of chirality, and weak and strong field quantum control. Developments and challenges in decoherence-sensitive condensed phase control as well as in bimolecular control are clearly described.

Indispensable for atomic, molecular and chemical physicists, physical chemists, materials scientists and nanotechnologists.

Leseprobe

Contents

Cover

Half Title page

Related Titles

Title page

Copyright page

Dedication

Preface to the Second Edition

Preface to the First Edition

Chapter 1: Preliminaries of the Interaction of Light with Matter

Chapter 2: Weak-Field Photodissociation

2.1 Photoexcitation of a Molecule with a Pulse of Light

2.2 State Preparation During the Pulse

2.3 Photodissociation

2.A Appendix: Molecular State Lifetime in Photodissociation

Chapter 3: Weak-Field Coherent Control

3.1 Traditional Excitation

3.2 Photodissociation from a Superposition State

3.3 The Principle of Coherent Control

3.4 Interference between N-Photon and M-Photon Routes

3.5 Polarization Control of Differential Cross Sections

3.6 Pump-Dump Control: Few Level Excitation

3.A Appendix: Mode-Selective Chemistry

Chapter 4: Control of Intramolecular Dynamics

4.1 Intramolecular Dynamics

Chapter 5: Optimal Control Theory

5.1 Pump-Dump Excitation with Many Levels: the Tannor–Rice Scheme

5.2 Optimal Control Theory

Chapter 6: Decoherence and Its Effects on Control

6.1 Decoherence

6.2 Sample Computational Results on Decoherence

6.3 Environmental Effects on Control: Some Theorems

6.4 Decoherence and Control

6.5 Countering Partially Coherent Laser Effects in Pump-Dump Control

6.6 Countering CW Laser Jitter

Chapter 7: Case Studies in Coherent Control

7.1 Two-Photon vs. Two-Photon Control

7.2 Control over the Refractive Index

7.3 The Molecular Phase in the Presence of Resonances

7.4 Control of Chaotic Dynamics

Chapter 8: Coherent Control of Bimolecular Processes

8.1 Fixed Energy Scattering: Entangled Initial States

8.2 Time Domain: Fast Timed Collisions

Chapter 9: The Interaction of Light with Matter: a Closer Look

9.1 Classical Electrodynamics of a Pulse of Light

9.2 The Dynamics of Quantized Particles and Classical Light Fields

Chapter 10: Coherent Control with Quantum Light

10.1 The Quantization of the Electromagnetic Field

10.2 Quantum Light and Quantum Interference

10.3 Quantum Field Control of Entanglement

10.4 Control of Entanglement in Quantum Field Chiral Separation

Chapter 11: Coherent Control beyond the Weak-Field Regime: Bound States and Resonances

11.1 Adiabatic Population Transfer

11.2 An Analytic Solution of the Nondegenerate Quantum Control Problem

11.3 The Degenerate Quantum Control Problem

11.4 Adiabatic Encoding and Decoding of Quantum Information

11.5 Multistate Piecewise Adiabatic Passage

11.6 Electromagnetically Induced Transparency

Chapter 12: Photodissociation Beyond the Weak-Field Regime

12.1 One-Photon Dissociation with Laser Pulses

12.2 Computational Examples

Chapter 13: Coherent Control Beyond the Weak-Field Regime: the Continuum

13.1 Control over Population Transfer to the Continuum by Two-Photon Processes

13.2 Pulsed Incoherent Interference Control

13.3 Resonantly Enhanced Photoassociation

13.4 Laser Catalysis

Chapter 14: Coherent Control of the Synthesis and Purification of Chiral Molecules

14.1 Principles of Electric Dipole Allowed Enantiomeric Control

14.2 Symmetry Breaking in the Two-Photon Dissociation of Pure States

14.3 Purification of Racemic Mixtures by “Laser Distillation”

14.4 Enantiomer Control: Oriented Molecules

14.5 Adiabatic Purification of Mixtures of Right-Handed and Left-Handed Chiral Molecules

14.A Appendix: Computation of B A B′ Enantiomer Selectivity 15 Strong-Field Coherent Control

Chapter 15: Strong-Field Coherent Control

15.1 Strong-Field Photodissociation with Continuous Wave Quantized Fields

15.2 Strong-Field Photodissociation with Pulsed Quantized Fields

15.3 Controlled Focusing, Deposition, and Alignment of Molecules

Chapter 16: Coherent Control with Few-Cycle Pulses

16.1 The Carrier Envelope Phase

16.2 Coherent Control and the CEO Frequency Measurement

16.3 The Recollision Model

16.4 CEP Stabilization and Control

16.5 Coherent Control of Sample Molecular Systems

Chapter 17: Case Studies in Optimal Control

17.1 Creating Excited States

17.2 Optimal Control in the Perturbative Domain

17.3 Adaptive Feedback Control

17.4 Analysis of Adaptive Feedback Experiments

17.5 Interference and Optimal Control

Chapter 18: Coherent Control in the Classical Limit

18.1 The One-Photon vs. Two-Photon Scenario Revisited

18.2 The Quartic Oscillator

18.3 Control in an Optical Lattice

Appendix Common Notation Used in the Book (in Order of Appearance)

References

Subject Index

Moshe Shapiro and Paul Brumer

Quantum Control of Molecular Processes

Related Titles

May, V., Kühn, O.Charge and Energy Transfer Dynamics in Molecular Systems2011ISBN: 978-3-527-40732-3Matta, C.F., Boyd, R.J. (eds.)The Quantum Theory of Atoms in MoleculesFrom Solid State to DNA and Drug Design2007ISBN: 978-3-527-30748-7Schleich, W. P., Walther, H. (eds.)Elements of Quantum Information2007ISBN: 978-3-527-40725-5Wilkening, G., Koenders, L.Nanoscale Calibration Standards and MethodsDimensional and Related Measurements in the Micro- and Nanometer Range2005ISBN: 978-3-527-40502-2Rice, S.A., Zhao, M.Optical Control of Molecular Dynamics2000ISBN: 978-0-471-35423-9

The Authors

Prof. Moshe ShapiroDepartment of ChemistryUniversity of British ColumbiaVancouver, British ColumbiaCanada V6T 1Z1

Prof. Paul BrumerDepartment of ChemistryUniversity of TorontoToronto, OntarioCanada M5S 3H6

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In memory of our parents and to our wives Rachelle and Abbey,

Preface to the First Edition

Despite its maturity, quantum mechanics remains one of the most intriguing of subjects. Since its emergence over 75 years ago, each generation has discovered, investigated, and utilized different attributes of quantum phenomena. In this book we introduce results from research over the past fifteen years that demonstrates that quantum attributes of light and matter afford the possibility of unprecedented control over the dynamics of atomic and molecular systems. This subject is the result of extensive investigations in chemistry and physics since 1985, and has seen enormous growth and interest over the past years. This growth reflects a confluence of developments – the maturation of quantum mechanics as a tool for chemistry and physics, the development of new laser devices that afford extraordinary facility in manipulating light, and the recognition that coherent laser light can be used to imprint information on atoms and molecules in a manner such that their subsequent dynamics leads towards desirable goals. As such, an appreciation of coherent control requires input from optical physics, physical chemistry, atomic and molecular physics, and quantum mechanics. This book aims to provide this background in a systematic manner, allowing the reader to gain expertise in the area.

We have written this monograph with the mature chemistry or physics graduate student in mind; the development is systematic, starting with the fundamental principles of light–matter interactions and concluding with a wide variety of specific topics. We endeavor to include a sufficient number of steps throughout the book to allow self-study or use in class. To retain the focus on the role of quantum interference in control, we tend to utilize examples from our own research, while including samples from that of others. This focus is partially made possible by the recent appearance of a comprehensive survey of the field by Rice and Zhao [2]. It is our expectation that the two books will complement one another.

This book is organized, after a discussion of light and light–matter interactions in Chapter 1, in order of increasing incident electromagnetic field strength. Chapters 2–8 primarily deal with molecular dynamics and control where the field strengths are such that perturbation theory is applicable. Emphasis is placed on the principle of coherent control, that is, control via quantum interference between simultaneous indistinguishable pathways to the same final state. From the view-point of chemistry, the vast majority of control work has thus far been done on photodissociation processes. As a consequence, we provide a thorough introduction to the dynamics of photodissociation in Chapter 2 and discuss its control in Chapters 2, 4 and 6. The extension of quantum control to bimolecular collision processes is provided in Chapter 7 and to the control of chirality (and asymmetric synthesis) in Chapter 8.

Applications of control using moderate fields are discussed in Chapters 9 to 11. These fields allow for new physical phenomena in both bound state and continuum problems, including adiabatic population transfer in both regimes, electromagnetically induced transparency in bound systems, as well as additional unimolecular and bimolecular control scenarios.

Strong fields introduce yet another set of phenomena allowing for the controlled manipulation of matter. Examples of light-induced potentials and the controlled focusing, alignment, and deposition of molecules are discussed in Chapter 12, after the introduction of the quantized electromagnetic field.

All of the quantum control scenarios involve a host of laser and system parameters. To obtain maximal control in any scenario necessitates a means of tuning the system and laser parameters to optimally achieve the desired objective. This topic, optimal control, is introduced and discussed in Chapters 4 and 13. The role of quantum interference effects in optimal control are discussed as well, providing a uniform picture of control via optimal pulse shaping and coherent control.

By definition, quantum control relies upon the unique quantum properties of light and matter, principally the wavelike nature of both. As such, maintenance of the phase information contained in both the matter and light is central to the success of the control scenarios. Chapter 5 deals with “decoherence”, that is, the loss of phase information due to the influence of the external environment in reducing the system coherence. Methods of countering decoherence are also discussed.

This book has benefited greatly from the research support that we have received over the past years. First, we acknowledge the ongoing support by the US Office of Naval Research through the research program of Dr. Peter J. Reynolds. We are also grateful to NSERC Canada, Photonics Research Ontario, the Israel Science Foundation and the Minerva Foundation, Germany. Equally importantly, we thank the many students and colleagues who have taken part in the development of coherent control and have contributed so much to the field. We wish the acknowledge Ignacio Franco, Einat Frishman, David Gerbasi, Michal Oren, and Alexander Pegarkov for comments on various parts of the manuscript, Ms. Susan Arbuckle for unstinting assistance with copyediting and indexing, Daniel Gruner for expert assistance on puzzling tex issues and Amnon Shapiro for preparing many of the postscript figure files. On a personal note, P.B. thanks Meir and Malka Cohen-Nehemia for training in the Mitzvah Technique that allowed him to counter the debilitating effects of back pain and body misuse.

None of this work would be possible without our wives, Rachelle and Abbey, who have provided the environment and support so necessary to allow productive science to be done. We are more than grateful to them both, as indicated in the dedication.

Finally, we welcome, at our email addresses below, any suggested corrections or additions to this book.

Rehovot, June 2002 Toronto, June 2002

Moshe Shapiro ([email protected])

Paul Brumer ([email protected])

Preface to the Second Edition

The growth of the field of the Quantum Control of Molecular Processes, emphasized in the preface of the first edition of this book, continues at an ever-increasing pace. Indeed, the past eight years have seen the explosive growth of both experimental and theoretical studies that are aimed at manipulating atomic and molecular processes at their most fundamental level. This updated book on Quantum Control captures important new directions and challenges in the area.

As in the first edition, our focus is on theories and experiments that utilize and reveal the underlying physics that is at the heart of quantum control. For this reason we provide only a minimal discussion of the purely mathematical aspects of control theory (amply covered, for example, in [1]). We also do not focus on modern adaptive feedback studies, which are extensively reviewed elsewhere (as indicated in Chapter 17), but which have yet to reveal conclusive physical insight into control mechanisms. Rather, this book stresses physical ideas that motivate control scenarios, and their resultant implementation.

Amongst other additions in this second edition, we include new approaches to the control of intramolecular dynamics (Chapter 4), a greatly extended treatment of decoherence and its affect on control (Chapter 6), a larger selection of sample coherent control scenarios (in Chapter 7), a detailed analysis of quantum control for collision processes (Chapter 8), a treatment of the very fundamentals of quantum interference in coherent control (Chapter 10), an extended discussion of coherent control via adiabatic passage (Chapter 11), a lengthy treatment of the control of chiral systems (Chapter 14), a Chapter on control with few-cycle “attosecond” pulses (Chapter 16), and an examination of coherent control in the classical limit (Chapter 18). In addition, numerous recent developments are described throughout the book, and several sections have been reorganized. We apologize to those whose work we could not cite; however, keeping this book of reasonable size necessitated (sometimes arbitrary) choices of material.

We express our continuing gratitude to our colleagues, postdocs, and students who have advanced this field of research. In addition, we are grateful for our own longstanding and continuing research collaboration, now lasting forty years, which has proven both fruitful and stimulating. We thank Ms. Susan Arbuckle for undertaking the myriad of annoying, important, and time-consuming tasks that must be completed before a volume can go to press. As always, she did an exceptional job. We thank Dr. Timur Grinev for outstanding proofreading, and for preparing an extensive table (to be found after Chapter 18) of the symbols used in this book. We thank Dr. Michael Spanner, NRC Ottawa for allowing use of his creative picture of lasers incident on a molecular chain, which graces the cover of this book. Sincere thanks also to NSERC, Canada for ongoing research support.

We have dedicated this book to our wives, who have provided the most essential of ingredients for scientific productivity, a stable and happy home environment.

Finally, we continue to welcome, at our email addresses below, any suggested corrections to this book.

Vancouver, March 2011 Toronto, March 2011

Moshe Shapiro ([email protected])

Paul Brumer ([email protected])

Chapter 3

Weak-Field Coherent Control

3.1 Traditional Excitation