Hydrogen Bonding and Transfer in the Excited State

By Ke-Li Han and Guang-Jiu Zhao

This book gives an extensive description of the state-of-the-art in research on excited-state hydrogen bonding and hydrogen transfer in recent years.

Initial chapters present both the experimental and theoretical investigations on the excited-state hydrogen bonding structures and dynamics of many organic and biological chromophores. Following this, several chapters describe the influences of the excited-state hydrogen bonding on various photophysical processes and photochemical reactions, for example: hydrogen bonding effects on fluorescence emission behaviors and photoisomerization; the role of hydrogen bonding in photosynthetic water splitting; photoinduced electron transfer and solvation dynamics in room temperature ionic liquids; and hydrogen bonding barrier crossing dynamics at bio-mimicking surfaces. Finally, the book examines experimental and theoretical studies on the nature and control of excited-state hydrogen transfer in various systems.

Hydrogen Bonding and Transfer in the Excited State is an essential overview of this increasingly important field of study, surveying the entire field over 2 volumes, 40 chapters and 1200 pages. It will find a place on the bookshelves of researchers in photochemistry, photobiology, photophysics, physical chemistry and chemical physics.

• Language: English
• Publisher: Wiley
• Release date: Mar 16, 2011
• ISBN: 9781119972921

Book preview

Contents

Cover

Title Page

Copyright

Editors' Biographies

Reviewer Comments

List of Contributors

Preface

Chapter 1: Vibrational Dynamics of the Double Hydrogen Bonds in Nucleic Acid Base Pairs

1.1 Introduction

1.2 Hydrogen Bonding and Nonlinear Infrared Spectroscopy

1.3 Correlated Vibrational Dynamics of an Adenine–Uracil Derivative in Solution

1.4 Conclusion

Acknowledgement

Appendix

References

Chapter 2: Vibrational Energy Relaxation Dynamics of XH Stretching Vibrations of Aromatic Molecules in the Electronic Excited State

2.1 Introduction

2.2 IR Spectra of 2-Naphthol and its H-Bonded Clusters in S1

2.3 VER Dynamics of Bare 2-Naphthol

2.4 VER Dynamics of H-Bonded Clusters of 2-Naphthol

2.5 Comparison of the cis → trans Barrier Height Between S0 and S1

2.6 Conclusion

References

Chapter 3: Hydrogen Bond Basicity in the Excited State: Concept and Applications

3.1 Introduction

3.2 Experiment

3.3 Results and Discussion

3.4 Summary

Acknowledgements

References

Chapter 4: Solute–Solvent Hydrogen Bond Formation in the Excited State. Experimental and Theoretical Evidence

4.1 Introduction

4.2 The Prerequisite Conditions for Hydrogen Bond Formation

4.3 Diagnosis Criteria and Quantitative Treatment of Hydrogen Bonds

4.4 Design of the Experiments

4.5 Theoretical Modelling of the H-Bonds

4.6 Conclusions

References

Chapter 5: Electronic-Excited-State Structures and Properties of Hydrated DNA Bases and Base Pairs

5.1 Introduction

5.2 Ground-State Structures of Nucleic Acid Bases and Base Pairs

5.3 Excited-State Structures of Nucleic Acid Bases

5.4 Excited States of Base Pairs

5.5 Excited-State Dynamics and Non-Radiative Decays

5.6 Conclusions

Acknowledgements

References

Chapter 6: Insight from Singlet into Triplet Excited-State Hydrogen Bonding Dynamics in Solution

6.1 Introduction

6.2 Theoretical Methods

6.3 Results and Discussion

6.4 Conclusion

Acknowledgements

References

Chapter 7: Probing Dynamic Heterogeneity in Nanoconfined Systems: the Femtosecond Excitation Wavelength Dependence and Fluorescence Correlation

7.1 Introduction

7.2 Solvation Dynamics in Nanoconfined Systems

7.3 Fluorescence Resonance Energy Transfer (FRET): λex Dependence

7.4 Excited-state Proton Transfer (ESPT)

7.5 Diffusion of Organic Dyes by Fluorescence Correlation Spectroscopy (FCS)

7.6 Conclusions

Acknowledgements

References

Chapter 8: Fluorescence Studies of the Hydrogen Bonding of Excited-State Molecules Within Supramolecular Host–Guest Inclusion Complexes

8.1 Introduction

8.2 Hydrogen Bonding Involving Excited States of Fluorescent Probes in Solution

8.3 Hydrogen Bonding of Excited States of Included Guests

8.4 Conclusions

References

Chapter 9: Hydrogen Bonding on Photoexcitation

9.1 Introduction

9.2 Intermolecular Excited-State Hydrogen Bonding

9.3 Concluding Remarks

References

Chapter 10: Effect of Intramolecular H-Bond-Type Interactions on the Photochemistry of Aza-Stilbene-Like Molecules

10.1 Introduction

10.2 Control of the Conformational Equilibria in the Ground State

10.3 Control of Radiative and Reactive Relaxation

10.4 Unusual Adiabatic Photoisomerization in the E → Z Direction

References

Chapter 11: Hydrogen Bonding Barrier-Crossing Dynamics at Biomimicking Surfaces

11.1 Introduction

11.2 Materials and Methods

11.3 Results and Discussion

11.4 Conclusion

Acknowledgements

References

Chapter 12: Intermolecular Hydrogen Bonding in the Fluorescence Excited State of Organic Luminophores Containing Both Carbonyl and Amino Groups

12.1 Introduction

12.2 Experimental

12.3 Results and Discussion

12.4 Conclusion

References

Chapter 13: Hydrogen-Bonding Effects on Excited States of Para-Hydroxyphenacyl Compounds

13.1 Introduction

13.2 Experimental and Computational Methods

13.3 Hydrogen-Bonding Effects on the Excited States of Selected Phenacyl Model Compounds

13.4 Hydrogen-Bonding Effects on the Excited States of Selected Para-Hydroxyphenacyl Ester Phototriggers and the Role of Water in the Deprotection and Subsequent Reactions

References

Chapter 14: Hydrogen-Bonding Effects on Intramolecular Charge Transfer

14.1 Introduction

14.2 Polarity and Viscosity

14.3 Hydrogen Bonding with the Donor Moiety

14.4 Hydrogen Bonding with the Acceptor Moiety

14.5 Conclusion

Acknowledgements

References

Chapter 15: Chemical Dynamics in Room-Temperature Ionic Liquids: the Role of Hydrogen Bonding

15.1 Photoinduced Electron Transfer in a Room-Temperature Ionic Liquid

15.2 Dynamics of Solvent Relaxation in Room-Temperature Ionic Liquids Containing Mixed Solvents

Acknowledgements

References

Chapter 16: Vibrational Spectroscopy for Studying Hydrogen Bonding in Imidazolium Ionic Liquids and their Mixtures with Cosolvents

16.1 Introduction

16.2 Experimental Approaches

16.3 Hydrogen Bonding in Ionic Liquids

16.4 Potential, Challenges and Future Applications

Acknowledgements

References

Chapter 17: Intramolecular H-Bond Formation Mediated De-Excitation of Curcuminoids: a Time-Resolved Fluorescence Study

17.1 Introduction

17.2 Experimental Set-Up and Data Analysis Methods

17.3 Results and Discussion

17.4 Conclusions

References

Chapter 18: Hydrogen Bonds of Protein-Bound Water Molecules in Rhodopsins

18.1 Introduction

18.2 Detection of Water Under Strongly Hydrogen-Bonded Conditions in Bacteriorhodopsin

18.3 Hydration Switch Model as a Proton Transfer Mechanism in the Schiff Base Region of Bacteriorhodopsin

18.4 Time-Resolved IR Study of Water Structural Changes in Bacteriorhodopsin at Room Temperature

18.5 Role of the Water Hydrogen Bond in a Chloride-Ion Pump

18.6 Strongly Hydrogen-Bonded Water Molecules and Functional Correlation with the Proton-Pump Activity

18.7 Conclusion

Acknowledgements

References

Chapter 19: Ground- and Excited-State Hydrogen Bonding in the Diazaromatic Betacarboline Derivatives

19.1 Introduction

19.2 MBC–HFIP and MHN–HFIP

19.3 BCA–HFIP

19.4 BC–HFIP

19.5 BC–BC and BC–PY

19.6 Concluding Remarks

Acknowledgements

References

Chapter 20: Effect of H-bonding on the Photophysical Behaviour of Coumarin Dyes

20.1 Introduction

20.2 Effect of Intermolecular H-bonding

20.3 Effect of Intramolecular H-bonding on ICT to TICT Conversion

20.4 Summary

References

Chapter 21: Role of Hydrogen Bonds in Photosynthetic Water Splitting

21.1 Introduction

21.2 Photosystem II: Overall Reaction Pattern and Cofactor Arrangement

21.3 Hydrogen Bonds and the Thermal Stability of PS II

21.4 Reaction Sequences of PS II and the Role of Hydrogen Bonds

21.5 Concluding Remarks and Future Perspectives

Acknowledgements

References

Chapter 22: Proton Transfer Reactions in the Excited Electronic State

22.1 Introduction

22.2 ESIPT in 3-Hydroxyflavones and Some Related Compounds

22.3 Dynamic Quenching of Fluorescence as a Simple Test for Study of Photochemical Reaction Character [87]

22.4 Use of Dynamic Quenching of Fluorescence for Study of Reactions from Higher Excited States

22.5 ESIPT from the S2 Singlet State in 3-Hydroxyflavone

22.6 Concluding Remarks

Acknowledgements

References

Chapter 23: Controlling Excited-State H-Atom Transfer Along Hydrogen-Bonded Wires

23.1 Introduction

23.2 Prototype System

23.3 What Favours/Prevents ESHAT

23.4 Conclusion

Acknowledgements

References

Chapter 24: Excited-State Proton Transfer via Hydrogen-Bonded Dimers and Complexes in Condensed Phase

24.1 Introduction

24.2 Biprotonic Transfer Within Doubly H-Bonded Homo- and Heterodimers

24.3 Proton Transfer Through Host/Guest Types of Hydrogen-Bonded Complexes

24.4 Solvation Dynamics Coupled into the Proton Transfer Reaction

24.5 Conclusions

References

Chapter 25: QM/MM Study of Excited-State Solvation Dynamics of Biomolecules

25.1 Introduction

25.2 Applications

25.3 Concluding Remarks

Acknowledgements

References

Chapter 26: Excited-State Intramolecular Proton Transfer Processes on Some Isomeric Naphthalene Derivatives: A Density Functional Theory Based Computational Study

26.1 Introduction

26.2 Theoretical Calculations

26.3 Results and Discussion

26.4 Conclusions

Acknowledgements

References

Chapter 27: Conformational Switching Between Acids and Their Anions by Hydrogen Bonding

27.1 Introduction

27.2 pKa Shift of Acids by Neighbouring Amide NH

27.3 Coordination of Anion Ligand to Metal Ion

27.4 Conclusions

References

Chapter 28: Charge Transfer in Excited States: ab initio Molecular Dynamics Simulations

28.1 Introduction

28.2 Charge-Transfer-to-Solvent-Driven Dissolution Dynamics of I−(H2O)2–5 Upon Excitation

28.3 Dynamics of Water Photolysis: Excited-State and Born–Oppenheimer Molecular Dynamics Study

28.4 Photodissociation of Hydrated Hydrogen Iodide Clusters: ab initio Molecular Dynamics Simulations

28.5 Excited-State Dynamics of Pyrrole–Water Complexes: ab initio Excited-State Molecular Dynamics Simulations

28.6 Conclusions

References

Chapter 29: Competitive ESIPT in o-Hydroxy Carbonyl Compounds: Perturbation Through Solvent Modulation and Internal Torsion

29.1 Excited-State Proton Transfer: An Overview

29.2 Excited-State Intramolecular Proton Transfer (ESIPT)

29.3 ESIPT in o-Hydroxy Carbonyl Compounds

29.4 Concluding Remarks

Acknowledgements

References

Chapter 30: Excited-State Double Hydrogen Bonding Induced by Charge Transfer in Isomeric Bifunctional Azaaromatic Compounds

30.1 Introduction

30.2 Pyrrolo-Quinoline Derivatives (PQ, DPC, TPC)

30.3 Methylene-Bridged 2-(2′-Pyridyl)indoles and Pyrido[2,3-a]carbazole (PC)

30.4 Fluorescence Quenching by Electron Transfer in Pyrroloquinolines and PyIn-n

30.5 Betacarboline Derivatives

30.6 Conclusions

References

Chapter 31: Hydrogen-Bonded Large Molecular Aggregates of Charged Amphiphiles and Unusual Rheology: Photochemistry and Photophysics of Hydroxyaromatic Dopants

31.1 Introduction

31.2 Microstructural Transition of Micelles in the Presence of Inorganic and Organic Salts

31.3 Microstructural Transition of Micelles in the Presence of Neutral Aromatic Dopants

31.4 Photochemistry and Photophysics of Hydroxyaromatic Compounds [87]

31.5 Excited-State Proton Transfer (ESPT) of Hydroxyaromatic Compounds

31.6 ESPT of Hydroxyaromatic Compounds in Organized Media and Some Unusual Emission Phenomena

31.7 Perspectives

Acknowledgements

References

Chapter 32: Excited-State Intramolecular Proton Transfer in 2-(20-Hydroxyphenyl)benzoxazole Derivatives

32.1 Introduction

32.2 Intramolecular Proton Transfer in 2,5-bis(2′-hydroxyphenyl)benzoxazole Derivatives

32.3 Summary and Future Prospects

References

Chapter 33: Ultrafast Dynamics of the Excited States of Hydrogen-Bonded Complexes and Solvation

33.1 Introduction

33.2 Identification and Characterization of Hydrogen-Bonded Complex

33.3 Vibrational Dynamics of the C=O Stretching Mode of Fluorenone

33.4 Dynamics of the Excited States of Hydrogen-Bonded Complex

33.5 Summary and Conclusion

33.6 Acknowledgement

References

Chapter 34: Volume Changes Associated with Solute–Solvent Reorganization Following Photoinduced Proton Transfer in Aqueous Solutions of 6-Methoxyquinoline

34.1 Introduction

34.2 Materials and Methods

34.3 Results and Discussion

References

Chapter 35: Molecular Recognition and Chemical Sensing of Anions Utilizing Excited-State Hydrogen-Bonding Interaction

35.1 Introduction

35.2 Recognition and Sensing of Anions by Intramolecular Hydrogen Bonding in Excited States

35.3 Recognition and Sensing of Anions by Intermolecular Hydrogen Bonding in Excited States

35.4 Recognition and Sensing of Anions by Conjugated Polymers through ESIPT

35.5 Concluding Remarks

References

Chapter 36: Theoretical Studies of Green and Red Fluorescent Proteins

36.1 Introduction

36.2 Method of Calculation

36.3 Results and Discussion

36.4 Conclusions and Future Work

Acknowledgements

References

Chapter 37: Changes in Active Site Hydrogen Bonding upon Formation of the Electronically Excited State of Photoactive Yellow Protein

37.1 Central Importance of Light in Biology

37.2 Possible Importance of Excited State Hydrogen Bonding in Photoreceptors

37.3 Introduction to Photoactive Yellow Protein

37.4 Hydrogen Bonding in the Initial State of PYP

37.5 Assignment of Vibrational Modes in PYP

37.6 Identification of Vibrational Structural Markers

37.7 Changes in Hydrogen Bonding During the Initial Stages of the PYP Photocycle

37.8 Sub-Picosecond Time-Resolved Transient Spectroscopy of PYP

37.9 Changes in Active Site Hydrogen Bonding upon the Formation of the S1 State of PYP

37.10 Excited State Proton Transfer in the Y42F Mutant of PYP

Acknowledgements

References

Chapter 38: Excited State Dynamics in the Light-Driven Enzyme Protochlorophyllide Oxidoreductase (POR)

38.1 Introduction

38.2 Protochlorophyllide Oxidoreductase (POR)

38.3 Catalytic Mechanism of POR

38.4 Ultrafast Catalytic Processes of the Isolated Pchlide Species

38.5 Ultrafast Catalytic Processes of the Enzyme-Bound Pchlide Species

38.6 Conclusions

References

Chapter 39: Photodissociation of Molecules in Pure and Doped Water and in Nitrogen Heterocyclic Clusters in the Excited State

39.1 Introduction

39.2 Experiment

39.3 Aqueous Photochemistry from the Cluster Perspective

39.4 Hydrogen Bonded Clusters of Nitrogen Heterocycles

39.5 General Conclusions and Outlook

Acknowledgements

References

Index

Title Page

This edition first published 2011

© 2011 John Wiley & Sons Ltd

Registered office

John Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, United Kingdom

For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book, please see our website at www.wiley.com

The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988.

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books.

Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought.

The publisher and the authors make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including, without limitation, any implied warranties of fitness for a particular purpose. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions.

The fact that an organization or website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or website may provide or recommendations it may make.

Further, readers should be aware that Internet websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work.

Neither the publisher nor the authors shall be liable for any damages arising herefrom.

Library of Congress Cataloging-in-Publication Data

Hydrogen bonding and transfer in the excited state / editors, Ke-Li Han, Guang-Jiu Zhao.

p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-66677-7 (cloth)

1. Hydrogen bonding. I. Han, Ke-Li. II. Zhao, Guang-Jiu.

QP517.H93E93 2010

572'.33–dc22

2010015107

Contents

Cover

Title Page

Copyright

Editors' Biographies

Reviewer Comments

List of Contributors

Preface

Chapter 1: Vibrational Dynamics of the Double Hydrogen Bonds in Nucleic Acid Base Pairs

1.1 Introduction

1.2 Hydrogen Bonding and Nonlinear Infrared Spectroscopy

1.3 Correlated Vibrational Dynamics of an Adenine–Uracil Derivative in Solution

1.4 Conclusion

Acknowledgement

Appendix

References

Chapter 2: Vibrational Energy Relaxation Dynamics of XH Stretching Vibrations of Aromatic Molecules in the Electronic Excited State

2.1 Introduction

2.2 IR Spectra of 2-Naphthol and its H-Bonded Clusters in S1

2.3 VER Dynamics of Bare 2-Naphthol

2.4 VER Dynamics of H-Bonded Clusters of 2-Naphthol

2.5 Comparison of the cis → trans Barrier Height Between S0 and S1

2.6 Conclusion

References

Chapter 3: Hydrogen Bond Basicity in the Excited State: Concept and Applications

3.1 Introduction

3.2 Experiment

3.3 Results and Discussion

3.4 Summary

Acknowledgements

References

Chapter 4: Solute–Solvent Hydrogen Bond Formation in the Excited State. Experimental and Theoretical Evidence

4.1 Introduction

4.2 The Prerequisite Conditions for Hydrogen Bond Formation

4.3 Diagnosis Criteria and Quantitative Treatment of Hydrogen Bonds

4.4 Design of the Experiments

4.5 Theoretical Modelling of the H-Bonds

4.6 Conclusions

References

Chapter 5: Electronic-Excited-State Structures and Properties of Hydrated DNA Bases and Base Pairs

5.1 Introduction

5.2 Ground-State Structures of Nucleic Acid Bases and Base Pairs

5.3 Excited-State Structures of Nucleic Acid Bases

5.4 Excited States of Base Pairs

5.5 Excited-State Dynamics and Non-Radiative Decays

5.6 Conclusions

Acknowledgements

References

Chapter 6: Insight from Singlet into Triplet Excited-State Hydrogen Bonding Dynamics in Solution

6.1 Introduction

6.2 Theoretical Methods

6.3 Results and Discussion

6.4 Conclusion

Acknowledgements

References

Chapter 7: Probing Dynamic Heterogeneity in Nanoconfined Systems: the Femtosecond Excitation Wavelength Dependence and Fluorescence Correlation

7.1 Introduction

7.2 Solvation Dynamics in Nanoconfined Systems

7.3 Fluorescence Resonance Energy Transfer (FRET): λex Dependence

7.4 Excited-state Proton Transfer (ESPT)

7.5 Diffusion of Organic Dyes by Fluorescence Correlation Spectroscopy (FCS)

7.6 Conclusions

Acknowledgements

References

Chapter 8: Fluorescence Studies of the Hydrogen Bonding of Excited-State Molecules Within Supramolecular Host–Guest Inclusion Complexes

8.1 Introduction

8.2 Hydrogen Bonding Involving Excited States of Fluorescent Probes in Solution

8.3 Hydrogen Bonding of Excited States of Included Guests

8.4 Conclusions

References

Chapter 9: Hydrogen Bonding on Photoexcitation

9.1 Introduction

9.2 Intermolecular Excited-State Hydrogen Bonding

9.3 Concluding Remarks

References

Chapter 10: Effect of Intramolecular H-Bond-Type Interactions on the Photochemistry of Aza-Stilbene-Like Molecules

10.1 Introduction

10.2 Control of the Conformational Equilibria in the Ground State

10.3 Control of Radiative and Reactive Relaxation

10.4 Unusual Adiabatic Photoisomerization in the E → Z Direction

References

Chapter 11: Hydrogen Bonding Barrier-Crossing Dynamics at Biomimicking Surfaces

11.1 Introduction

11.2 Materials and Methods

11.3 Results and Discussion

11.4 Conclusion

Acknowledgements

References

Chapter 12: Intermolecular Hydrogen Bonding in the Fluorescence Excited State of Organic Luminophores Containing Both Carbonyl and Amino Groups

12.1 Introduction

12.2 Experimental

12.3 Results and Discussion

12.4 Conclusion

References

Chapter 13: Hydrogen-Bonding Effects on Excited States of Para-Hydroxyphenacyl Compounds

13.1 Introduction

13.2 Experimental and Computational Methods

13.3 Hydrogen-Bonding Effects on the Excited States of Selected Phenacyl Model Compounds

13.4 Hydrogen-Bonding Effects on the Excited States of Selected Para-Hydroxyphenacyl Ester Phototriggers and the Role of Water in the Deprotection and Subsequent Reactions

References

Chapter 14: Hydrogen-Bonding Effects on Intramolecular Charge Transfer

14.1 Introduction

14.2 Polarity and Viscosity

14.3 Hydrogen Bonding with the Donor Moiety

14.4 Hydrogen Bonding with the Acceptor Moiety

14.5 Conclusion

Acknowledgements

References

Chapter 15: Chemical Dynamics in Room-Temperature Ionic Liquids: the Role of Hydrogen Bonding

15.1 Photoinduced Electron Transfer in a Room-Temperature Ionic Liquid

15.2 Dynamics of Solvent Relaxation in Room-Temperature Ionic Liquids Containing Mixed Solvents

Acknowledgements

References

Chapter 16: Vibrational Spectroscopy for Studying Hydrogen Bonding in Imidazolium Ionic Liquids and their Mixtures with Cosolvents

16.1 Introduction

16.2 Experimental Approaches

16.3 Hydrogen Bonding in Ionic Liquids

16.4 Potential, Challenges and Future Applications

Acknowledgements

References

Chapter 17: Intramolecular H-Bond Formation Mediated De-Excitation of Curcuminoids: a Time-Resolved Fluorescence Study

17.1 Introduction

17.2 Experimental Set-Up and Data Analysis Methods

17.3 Results and Discussion

17.4 Conclusions

References

Chapter 18: Hydrogen Bonds of Protein-Bound Water Molecules in Rhodopsins

18.1 Introduction

18.2 Detection of Water Under Strongly Hydrogen-Bonded Conditions in Bacteriorhodopsin

18.3 Hydration Switch Model as a Proton Transfer Mechanism in the Schiff Base Region of Bacteriorhodopsin

18.4 Time-Resolved IR Study of Water Structural Changes in Bacteriorhodopsin at Room Temperature

18.5 Role of the Water Hydrogen Bond in a Chloride-Ion Pump

18.6 Strongly Hydrogen-Bonded Water Molecules and Functional Correlation with the Proton-Pump Activity

18.7 Conclusion

Acknowledgements

References

Chapter 19: Ground- and Excited-State Hydrogen Bonding in the Diazaromatic Betacarboline Derivatives

19.1 Introduction

19.2 MBC–HFIP and MHN–HFIP

19.3 BCA–HFIP

19.4 BC–HFIP

19.5 BC–BC and BC–PY

19.6 Concluding Remarks

Acknowledgements

References

Chapter 20: Effect of H-bonding on the Photophysical Behaviour of Coumarin Dyes

20.1 Introduction

20.2 Effect of Intermolecular H-bonding

20.3 Effect of Intramolecular H-bonding on ICT to TICT Conversion

20.4 Summary

References

Chapter 21: Role of Hydrogen Bonds in Photosynthetic Water Splitting

21.1 Introduction

21.2 Photosystem II: Overall Reaction Pattern and Cofactor Arrangement

21.3 Hydrogen Bonds and the Thermal Stability of PS II

21.4 Reaction Sequences of PS II and the Role of Hydrogen Bonds

21.5 Concluding Remarks and Future Perspectives

Acknowledgements

References

Chapter 22: Proton Transfer Reactions in the Excited Electronic State

22.1 Introduction

22.2 ESIPT in 3-Hydroxyflavones and Some Related Compounds

22.3 Dynamic Quenching of Fluorescence as a Simple Test for Study of Photochemical Reaction Character [87]

22.4 Use of Dynamic Quenching of Fluorescence for Study of Reactions from Higher Excited States

22.5 ESIPT from the S2 Singlet State in 3-Hydroxyflavone

22.6 Concluding Remarks

Acknowledgements

References

Chapter 23: Controlling Excited-State H-Atom Transfer Along Hydrogen-Bonded Wires

23.1 Introduction

23.2 Prototype System

23.3 What Favours/Prevents ESHAT

23.4 Conclusion

Acknowledgements

References

Chapter 24: Excited-State Proton Transfer via Hydrogen-Bonded Dimers and Complexes in Condensed Phase

24.1 Introduction

24.2 Biprotonic Transfer Within Doubly H-Bonded Homo- and Heterodimers

24.3 Proton Transfer Through Host/Guest Types of Hydrogen-Bonded Complexes

24.4 Solvation Dynamics Coupled into the Proton Transfer Reaction

24.5 Conclusions

References

Chapter 25: QM/MM Study of Excited-State Solvation Dynamics of Biomolecules

25.1 Introduction

25.2 Applications

25.3 Concluding Remarks

Acknowledgements

References

Chapter 26: Excited-State Intramolecular Proton Transfer Processes on Some Isomeric Naphthalene Derivatives: A Density Functional Theory Based Computational Study

26.1 Introduction

26.2 Theoretical Calculations

26.3 Results and Discussion

26.4 Conclusions

Acknowledgements

References

Chapter 27: Conformational Switching Between Acids and Their Anions by Hydrogen Bonding

27.1 Introduction

27.2 pKa Shift of Acids by Neighbouring Amide NH

27.3 Coordination of Anion Ligand to Metal Ion

27.4 Conclusions

References

Chapter 28: Charge Transfer in Excited States: ab initio Molecular Dynamics Simulations

28.1 Introduction

28.2 Charge-Transfer-to-Solvent-Driven Dissolution Dynamics of I−(H2O)2–5 Upon Excitation

28.3 Dynamics of Water Photolysis: Excited-State and Born–Oppenheimer Molecular Dynamics Study

28.4 Photodissociation of Hydrated Hydrogen Iodide Clusters: ab initio Molecular Dynamics Simulations

28.5 Excited-State Dynamics of Pyrrole–Water Complexes: ab initio Excited-State Molecular Dynamics Simulations

28.6 Conclusions

References

Chapter 29: Competitive ESIPT in o-Hydroxy Carbonyl Compounds: Perturbation Through Solvent Modulation and Internal Torsion

29.1 Excited-State Proton Transfer: An Overview

29.2 Excited-State Intramolecular Proton Transfer (ESIPT)

29.3 ESIPT in o-Hydroxy Carbonyl Compounds

29.4 Concluding Remarks

Acknowledgements

References

Chapter 30: Excited-State Double Hydrogen Bonding Induced by Charge Transfer in Isomeric Bifunctional Azaaromatic Compounds

30.1 Introduction

30.2 Pyrrolo-Quinoline Derivatives (PQ, DPC, TPC)

30.3 Methylene-Bridged 2-(2′-Pyridyl)indoles and Pyrido[2,3-a]carbazole (PC)

30.4 Fluorescence Quenching by Electron Transfer in Pyrroloquinolines and PyIn-n

30.5 Betacarboline Derivatives

30.6 Conclusions

References

Chapter 31: Hydrogen-Bonded Large Molecular Aggregates of Charged Amphiphiles and Unusual Rheology: Photochemistry and Photophysics of Hydroxyaromatic Dopants

31.1 Introduction

31.2 Microstructural Transition of Micelles in the Presence of Inorganic and Organic Salts

31.3 Microstructural Transition of Micelles in the Presence of Neutral Aromatic Dopants

31.4 Photochemistry and Photophysics of Hydroxyaromatic Compounds [87]

31.5 Excited-State Proton Transfer (ESPT) of Hydroxyaromatic Compounds

31.6 ESPT of Hydroxyaromatic Compounds in Organized Media and Some Unusual Emission Phenomena

31.7 Perspectives

Acknowledgements

References

Chapter 32: Excited-State Intramolecular Proton Transfer in 2-(20-Hydroxyphenyl)benzoxazole Derivatives

32.1 Introduction

32.2 Intramolecular Proton Transfer in 2,5-bis(2′-hydroxyphenyl)benzoxazole Derivatives

32.3 Summary and Future Prospects

References

Chapter 33: Ultrafast Dynamics of the Excited States of Hydrogen-Bonded Complexes and Solvation

33.1 Introduction

33.2 Identification and Characterization of Hydrogen-Bonded Complex

33.3 Vibrational Dynamics of the C=O Stretching Mode of Fluorenone

33.4 Dynamics of the Excited States of Hydrogen-Bonded Complex

33.5 Summary and Conclusion

33.6 Acknowledgement

References

Chapter 34: Volume Changes Associated with Solute–Solvent Reorganization Following Photoinduced Proton Transfer in Aqueous Solutions of 6-Methoxyquinoline

34.1 Introduction

34.2 Materials and Methods

34.3 Results and Discussion

References

Chapter 35: Molecular Recognition and Chemical Sensing of Anions Utilizing Excited-State Hydrogen-Bonding Interaction

35.1 Introduction

35.2 Recognition and Sensing of Anions by Intramolecular Hydrogen Bonding in Excited States

35.3 Recognition and Sensing of Anions by Intermolecular Hydrogen Bonding in Excited States

35.4 Recognition and Sensing of Anions by Conjugated Polymers through ESIPT

35.5 Concluding Remarks

References

Chapter 36: Theoretical Studies of Green and Red Fluorescent Proteins

36.1 Introduction

36.2 Method of Calculation

36.3 Results and Discussion

36.4 Conclusions and Future Work

Acknowledgements

References

Chapter 37: Changes in Active Site Hydrogen Bonding upon Formation of the Electronically Excited State of Photoactive Yellow Protein

37.1 Central Importance of Light in Biology

37.2 Possible Importance of Excited State Hydrogen Bonding in Photoreceptors

37.3 Introduction to Photoactive Yellow Protein

37.4 Hydrogen Bonding in the Initial State of PYP

37.5 Assignment of Vibrational Modes in PYP

37.6 Identification of Vibrational Structural Markers

37.7 Changes in Hydrogen Bonding During the Initial Stages of the PYP Photocycle

37.8 Sub-Picosecond Time-Resolved Transient Spectroscopy of PYP

37.9 Changes in Active Site Hydrogen Bonding upon the Formation of the S1 State of PYP

37.10 Excited State Proton Transfer in the Y42F Mutant of PYP

Acknowledgements

References

Chapter 38: Excited State Dynamics in the Light-Driven Enzyme Protochlorophyllide Oxidoreductase (POR)

38.1 Introduction

38.2 Protochlorophyllide Oxidoreductase (POR)

38.3 Catalytic Mechanism of POR

38.4 Ultrafast Catalytic Processes of the Isolated Pchlide Species

38.5 Ultrafast Catalytic Processes of the Enzyme-Bound Pchlide Species

38.6 Conclusions

References

Chapter 39: Photodissociation of Molecules in Pure and Doped Water and in Nitrogen Heterocyclic Clusters in the Excited State

39.1 Introduction

39.2 Experiment

39.3 Aqueous Photochemistry from the Cluster Perspective

39.4 Hydrogen Bonded Clusters of Nitrogen Heterocycles

39.5 General Conclusions and Outlook

Acknowledgements

References

Index

Editors' Biographies

Ke-Li Han was born in 1963 in Shandong Province, China. He received his doctorate in 1990 from the State Key Laboratory of Molecular Reaction Dynamics at the Dalian Institute of Chemical Physics and subsequently became an assistant professor at the Dalian Institute of Chemical Physics. He pursued postdoctoral studies at the Emory University and the University of California at Davis in the years 1993–1995. In 1995, he became a full professor of Chemical Physics at the State Key Laboratory of Molecular Reaction Dynamics at the Dalian Institute of Chemical Physics. He was also an adjunct professor at the Dalian University of Technology and Shandong University and a visiting professor at the University of Melbourne, the City University of Hong Kong, the National University of Singapore, the University of California at Berkeley, New York University, the University of Bristol, and so on.

Professor Han received the Outstanding Young Scientist award from the National Natural Science Foundation of China in 1998 and the Natural Science Prize (first class) of the Chinese Academy of Sciences and the Young Chemist Prize of the Chinese Chemical Society in 1999, as well as the Natural Science Prize (first class) of Liaoning Province in 2005. His own achievements have been published in over 300 publications. Professor Han's current research interests involve experimental and theoretical chemical dynamics, including non-adiabatic reaction dynamics of small molecules, the photodissociation dynamics of gas-phase molecules, the excited-state hydrogen-bonding dynamics of large molecules in solution, biochemical reaction mechanisms and dynamics catalysed by enzymes.

Guang-Jiu Zhao was born in 1980 in Hebei Province, China. He received his bachelor's degree in Material Engineering in 2003 at the Dalian University of Technology. He received his doctorate in Chemical Physics in 2008 from the State Key Laboratory of Molecular Reaction Dynamics at the Dalian Institute of Chemical Physics. Subsequently, he became an assistant professor at the Dalian Institute of Chemical Physics. In 2009, he was promoted to associate professor at the Dalian Institute of Chemical Physics. He has won the Chinese Academy of Sciences Director Award in 2009, the Natural Sciences Research Award of Liaoning Province in 2008, the Lu-Jiaxi Award for Chinese Excellent Graduate Student in 2007, and so on. His research interests are focused on excited-state hydrogen bonding and hydrogen transfer in photophysics, photochemistry and photobiology by the use of combined experimental and theoretical methods.

Reviewer Comments

Professor Richard N. Zare

Chair of the Department of Chemistry, Stanford University, USA

Hydrogen bonding has always been a bit of a mystery to me, it having the character of directionality but being an order of magnitude or more weaker than a typical covalent bond. Hydrogen bonding can occur between molecules or between different parts of the same molecule. At last, we have a compilation of studies concerning hydrogen bonding and hydrogen transfer reaction in excited-state species, a most welcome addition to the literature on this important topic. I commend the reading of this monograph to all chemists.

Professor Donald G. Truhlar

Associate Editor of the Journal of the American Chemical Society, Regents Professor of Chemistry, Chemical Physics, Nanoparticle Science and Engineering, and Scientific Computation, Department of Chemistry, University of Minnesota, USA

I have just completed looking at the preface, contents and abstracts of the new book on excited-state hydrogen bonding. Although this area is very important in both biological and technological chemistry, the field has been hampered by the lack of a monograph. The book you have assembled is very impressive, with contributions from a remarkably broad set of groups working in this kind of research. I was especially pleased to see that the coverage includes both standard topics and unusual ones, such as hydrogen bonding in triplet states, which is a very interesting subject, and hydrogen bonding in ionic liquids. The book is sure to become a classic in the field.

Professor Wolfgang Domcke

Chief Editor of Chemical Physics, Chair of Theoretical Chemistry, Department of Chemistry, Technical University of Munich, D-85747 Garching, Germany

I have read the tables of contents and the abstracts of the book chapters. This book gives an impressively broad overview of the current research on excited-state hydrogen bonding in chemistry. Numerous organic chromophores and their intramolecular as well as intermolecular hydrogen and/or proton transfer dynamics are discussed in detail. DNA bases, base pairs and photoactive proteins are considered, as well as basic features of the photosynthetic reaction centre and of the photochemistry of water itself. Interesting aspects that are somewhat underrepresented are the role of hydrogen bonds in the excited-state dynamics of peptides and of protonated peptides, the zwitterionic forms of amino acids in water, as well as hydrogen transfer reactions in hydrogen-bonded chromophore–solvent clusters in supersonic jets. Overall, the book represents a good balance of experimental and computational research. The book provides an excellent introduction to an important contemporary research topic for graduate students as well as for experienced researchers.

Professor Andrjez Sobolweski

Institute of Physics, Polish Academy of Science, Poland

Thank you very much for your invitation to review the book. As I was in touch with Wolfgang Domcke at the time he was reviewing this book, I am already familiar with this proposal, and my opinion is in line with his comments, including his reservations. Generally, I think the book represents a really good introduction to the topic for a broader readership.

Professor C.N.R. Rao

Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, India

It is nice that we have a much-needed book on excited-state hydrogen bonding. This is most welcome and will be useful to workers in the field.

Professor Kankan Bhattacharyya

Senior Editor of The Journal of Physical Chemistry, Director of the Indian Association for the Cultivation of Science, Kolkata, India

This is a comprehensive text that summarizes the latest developments in hydrogen bonding and its role in many fundamental issues. I liked the wide range of topics covered. The 39 chapters spread over nearly 1200 pages dealt with many systems that range from proteins, ionic liquids and micelles to ultracold vapour in supersonic jets. Many spectroscopic (electronic and vibrational) and microscopic techniques with very high temporal and spectral resolution have been used. The primary aim of these volumes is to focus on hydrogen bonding. Implications of this in many issues, such as solvation dynamics, proton/charge transfer and FRET, have been discussed. This will be an excellent textbook and reference material for graduate students and research scientists.

Professor Jun Zeng

Guest Professor, Sichuan University, China, and Chief Scientific Officer, Qubist Molecular Design, Australia

This is probably the first book that presents comprehensive reviews on the recent theoretical and experimental investigations on the nature of excited-state hydrogen bonding and hydrogen transfers and their influences on many aspects of photophysics, photochemistry and photobiology. From this book, readers will gain much insightful information on the structure, dynamics and spectroscopic properties of hydrogen bonding in the excited states of many important chemical and biological systems. A very useful reference book!

Professor Steven D. Schwartz

Biophysics and Biochemistry, Albert Einstein College of Medicine, USA

This volume promises to be of significant value. Proton transfers are ubiquitous in both complex condensed phases as hydrogen bonds and in biological systems both as hydrogen bonds and as (one of) the chemical steps in enzymatic reactions in biology. In addition, biotechnology through such reactants as GFP is critically dependent on hydrogen transfer. This volume, containing both experiment and theory, promises many useful reviews and new results. In addition, for a western audience, the volume has the advantage of including authors well known to the American audience and others whose work will be new.

Professor Hans Lischka

Institute for Theoretical Chemistry, University of Vienna, Waehringerstrasse 17, A-1090 Vienna, Austria

I have read the Table of Contents of your book Hydrogen Bonding and Transfer in the Excited State with great interest. It contains excellent chapters written by leading world scientists. I am sure that the book will be a great success.

Professor Chang-Guo Zhan

Department of Pharmaceutical Sciences, University of Kentucky, USA

I am pleased to read your detailed plan for a book entitled Hydrogen Bonding and Transfer In the Excited State. I think this will be an important book that covers all aspects of hydrogen bonding and hydrogen transfer in excited states. The book will be very interesting for all scientists in the field of chemistry, biochemistry and biophysics who are interested in hydrogen bonding or hydrogen transfer in excited states. I hope this book will be published as soon as possible.

Professor Jeffrey R. Reimers

ARC Professorial Research Fellow, School of Chemistry F11, The University of Sydney, Sydney NSW 2006, Australia

Biochemical structure and function always involve a delicately controlled balance of hydrophobic and hydrophilic forces. While the hydrophobic force is non-specific and always present, the hydrogen-bonding interactions that empower the hydrophilic forces are specific and directed. They are critical to molecular recognition, driving the secondary structure of proteins and the helix formation of DNA. But life is more than biological structure – it is dynamics and motion, metabolism and vitality. What happens to hydrogen bonds in systems with excess energy? Can molecular recognition be modified and a cascade of biological processes ensue? How are proteins and DNA modified when molecules absorb light? Sometimes a change just happens from one possible tautomeric form to another, sometimes whole new motifs like strong hydrogen bonding to aromatics occurs. How quickly do these processes occur, how quickly is the energy dissipated and how quickly does the system return to normal? This is the first book to review excited-state hydrogen bonding, detailing the great variety of consequences found. It provides new insights into the very nature of the forces that create secondary structure in chemistry and biology.

Professor Zhi-Ru Li

State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, China

Hydrogen bonding plays an important role in chemistry, biology and physics. Research on excited-state hydrogen bonding and hydrogen transfer is a novel field. Excited-state hydrogen bonding and hydrogen transfer play significant roles in many photophysical processes and photochemical reactions. This book includes 39 chapters covering various frontier areas of excited-state hydrogen bonding. The contents of this book are very rich. This is very beneficial for researchers and graduate students who are interested in the fields of molecular and supramolecular photochemistry, photobiology and photophysics.

Professor Shengli Zou

Chemistry Department, University of Central Florida, USA

Hydrogen bonding is one of the most important and complex interactions between different molecules or different groups in a big molecule, especially a biomolecule. Understanding the roles of hydrogen bonding in chemical reactions, proton transfer and charge transfer is crucial in revealing the mechanism of these processes. The authors address hydrogen-bonding-induced charge transfer, conformational switching between acids and their anions and controlled intramolecular proton transfer. The importance of hydrogen bonding in photosynthetic water splitting and green fluorescence protein is also discussed. The investigation of hydrogen bonding involving electronically excited molecules is a substantial challenge both experimentally and theoretically. There are few books focusing on hydrogen bonding of molecules in excited states owing to the complexity of the system, especially for theoretical calculations. The proposed book will be a helpful reference book for research groups interested in understanding hydrogen bonding in different environments and processes. The book is highly recommended for publication.

Professor Anna Spalletti

Dipartimento di Chimica, Università di Perugia, 06123 Perugia, Italy

Thank you for the information about the new book on hydrogen bonding. My coauthors and I congratulate you on your success in collecting, in a relatively short time, such abundant material (39 contributions!) on a variety of aspects of HB effects on the spectral, photophysical and photochemical properties of so many different organic compounds. From a glance through the abstracts we did not notice any omission. Some discrepancies (for example, in the length of the chapters) and repetitions will certainly be present, but this is bound to happen in such a large review work. Best wishes for the success of the book.

Professor Noam Agmon

Institute of Chemistry, Hebrew University, Jerusalem

The skeleton of the new book looks very impressive in its scope: 39 chapters by world experts covering different aspects of excited-state dynamics within hydrogen-bonded systems. At this stage, when only abstracts are available, it is hard to say more, but I am definitely waiting eagerly for this project to appear in print, as I believe it will be an important milestone for those working in the field and those considering doing so.

Professor Gernot Renger

Max-Volmer-Laboratorium für Biophysikalische Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany

Hydrogen bonds are the most important structural determinants in nature. Striking examples of the paramount role of hydrogen bonds are the unique properties of water and the structure of DNA and proteins. The functional relevance of hydrogen bonds is clearly illustrated by their participation in proton transfer mechanisms (e.g. the Grotthus mechanism, proton-transfer-coupled electron transfer, etc.). Of special interest in basic research are the properties of hydrogen bonds in electronically and vibronically excited molecules. This book is an excellent summary of our current stage of knowledge on the different facets of hydrogen bonding which plays a central role for the interaction between molecules. It covers, in 39 chapters, a wide field of topics ranging from the basic properties of hydrogen bonds in comparatively simple electronically excited pigments to the role in complicated biological systems like rhodopsins and photosynthetic water splitting. This book will find a broad audience. It is of great value for scientists working on various aspects of hydrogen bonding. It provides, in a single publication, a nice overview of such a wide field of different topics.

Professor Jingwen Chen

Key Laboratory of Industrial Ecology and Environmental Engineering, Department of Environmental Science and Technology, Dalian University of Technology, Linggong Road 2, Dalian 116024, China

Hydrogen bonding determines the properties and activities of many compounds, which is of great importance in chemistry, biology, physics and environmental science. Electronically excited-state hydrogen bonding and hydrogen transfer play an increasingly important role in many photophysical processes and photochemical reactions. In the field of environmental science, studies in recent decades have proved that photodegradation is an important transformation or degradation pathway for toxic organic compounds in aquatic and atmospheric environments, and environmental media have great effects on the photodegradation kinetics and pathways. In some cases, environmental media were observed to influence the photodegradation via hydrogen bonding or hydrogen transfer. Excited-state hydrogen bonding and hydrogen transfer may determine the indirect/direct photodegradation kinetics and pathways of many organic pollutants, including halogenated aromatic compounds (e.g. polychlorinated dibenzo-p-dioxin/dibenzofurans, polychlorinated biphenyls, polybrominated diphenyl ethers), pesticides, pharmaceutical and personal care products, etc. Excited-state hydrogen bonding and hydrogen transfer may also have great impacts on the photoinduced toxicities of organic pollutants. This monograph will be the first to deal with hydrogen bonding in excited states, presenting an extensive description of the research progress on excited-state hydrogen bonding and hydrogen transfer in recent years. Both experimental and theoretical investigations on excited-state hydrogen-bonding structures and dynamics of many organic and biological chromophores are included. There are also several chapters describing the influences of excited-state hydrogen bonding and hydrogen transfer on various photophysical processes and photochemical reactions. Thus, this book will be very helpful in understanding the nature of hydrogen bonding in relevant areas and in understanding the photochemical transformation/photoinduced toxicity of environmental organic pollutants.

Professor Brian D. Wagner

3M Canada National Teaching Fellow, Department of Chemistry, University of Prince Edward Island, Charlottetown, PE C1A 4P3, Canada

I am very impressed by the comprehensive coverage represented by the many chapters in this two-volume set. All of the major topics and considerations involving hydrogen bonding of excited states have been covered. This will be a very useful set of books for a wide range of researchers. I am proud to have been able to make a contribution to the book.

Professor Hiroshi Sekiya

Department of Chemistry, Faculty of Science, Kyushu Unviversity, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

This book covers a very wide range of topics on hydrogen-bonding and excited-state proton/hydrogen transfer reactions in various molecules and molecular clusters developed by spectroscopic meaasurements and theoretical studies. Many of the results are quite new and interesting for physists, chemists and biologists. I would like to recommend this book for many young and senior researchers interested in the intriguing field of hydrogen bonds and proton/hydrogen transfer reactions.

Professor James C. Crabbe

Professor of Biochemistry, Dean of the Faculty of Creative Arts, Technologies and Science, University of Bedfordshire, Park Square, Luton LU1 3JU, UK

This is an exciting new publication on one of the key elements of life – the hydrogen bond. The authors have produced an array of exciting chapters on hydrogen bonding and hydrogen transfer, covering many aspects of chemistry and biochemistry. This will be an important reference work for many years to come.

Professor Takayuki Ebata

Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan

This book covers recent experimental and theoretical studies on the dynamics of H-bonded systems from the simple aromatic molecules to real biomolecules. An interesting point is that it concentrates on the topic of the electronic excited state, which is different from other books published so far. In this sense, I think (and hope) this book will attract people in a variety of fields.

Professor Jianzhang Zhao

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China

This book focuses on excited-state hydrogen bonding and proton transfer. The chapters cover a wide range from the formation of the hydrogen bond in the excited state to the fate of the hydrogen bond in the excited state, such as ESIPT (excited-state intramolecular proton transfer) and vibration dissipation of excited-state energy. Experimental as well as theoretical methods are employed to elucidate hydrogen bonding in the excited state, such as time-resolved vibrational spectra and ab initio or DFT calculations. The subjects involved in the discussion are very diverse, ranging from small organic molecules (such as fluorescent dyes) to biological systems (such as DNA). Therefore, I believe this book addresses most of the research topics of excited-state hydrogen bonding, and the publication of the book will be of significance for the scientific community.

Professor Mihaela Hillebrand

Department of Physical Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta 4-12, Bucharest, Romania

The book encompasses the latest achievements in excited-state hydrogen-bonded systems by means of experimental and computational methods. The papers collected provide a good insight into how advances in ultrafast spectroscopic techniques and state-of-the-art quantum chemical calculations have opened up new perspectives on excited-state processes, namely hydrogen bond formation and hydrogen bond transfer in a wide range of chemical and biochemical hydrogen-bonded systems, from molecules, clusters or complexes to biopolymers. It is the first monograph devoted to this subject, and its publication is worthwhile from two points of view – the overall subject and the content. Firstly, considering the importance of hydrogen bond formation in many chemical and biochemical processes and the difficulties related to a good understanding of the excited-state photophysics, a comprehensive treatment of the subject is necessary. Secondly, the book covers most of the aspects of the topic and is characterized by a good balance between a review of up-to-date literature data and some new results. The book benefits from contributions by renowned scientists with acknowledged results in the field. The editors, remarkably, have succeeded in putting together theoretical aspects involved in excited-state hydrogen photodynamics and possible applications. The book Hydrogen Bonding and Transfer in the Excited State will be a good tool both for researchers in the field and for graduate students.

Professor Samir Kumar Pal

Unit for Nano Science & Technology, Department of Chemical, Biological & Macromolecular Sciences, S.N. Bose National Centre for Basic Sciences, Block JD, Sector III, Salt Lake, Kolkata 700098, India

The book proposal, entitled Hydrogen Bonding and Transfer in the Excited State and edited by Ke-Li Han and Guang-Jiu Zhao, consists of 39 chapters contributed by eminent scientists in this field from all over the world. The contributions embodied here are mostly based on experimental results, along with six papers based on theoretical calculations and simulation results. The theme of the proposed book is very interesting, as many of the fundamental processes in photophysics and photobiology occur in the excited states and involve formation and/or rupture of the hydrogen bonds (HB). A very popular example of such a process is the water splitting in photosynthesis. Ultrafast proton transfer (PT) also serves as the key reaction in many important processes. Unfortunately, there has been no such monograph in the present literature that discusses the various aspects of HB and PT in the excited state. In this regard, this attempt to gather important information on HB and PT within a single cover is very encouraging. The proposed book mainly consists of experimental results obtained from steady-state and time-resolved fluorescence studies, as this technique extracts the maximum valuable information on the excited state. Other experimental techniques dealt within the book are UV-IR double-resonance excitation, time-resolved resonance Raman spectroscopy, time-resolved FTIR, etc. The related changes in basicity, solvation, hydrogen bond dynamics and other fundamental photophysical and photochemical properties of fluoroprobes upon excitation are discussed and reviewed in many chapters (e.g. Chapters 3, 5, 6, 7, 20, 31, etc.). Intermolecular charge transfer (ICT) is discussed in Chapters 4 and 14. The excited-state photochemistry and photophysics of many organic molecules are discussed in Chapters 12, 13, 19, 25, 27, 30 and 32. Excited-state PT and energy transfer (ET) in different molecules and solvents are discussed in Chapters 10, 17, 19, 22, 23, 24, 27, 29, 32, 33 and 34. Chapters 15 and 16 deal with the hydrogen-bonding dynamics in room-temperature ionic liquids (IL). HB barrier-crossing dynamics in nanoconfinement is discussed in Chapter 11. Excited-state HB in biologically important molecules like nucleic acids (Chapters 1 and 9), bacteriorhodopsin (Chapter 18), green fluorescent protein (Chapter 34) and photoconductive yellow protein (Chapter 35), as well as in some complex systems like host–guest complexes (Chapter 8), worm-like micelles (Chapter 29) and clusters (Chapters 1, 2, 26 and 37), is also discussed. Some very interesting topics involving excited-state HB and PT, like the water splitting process in photosynthesis (Chapter 21), excited-state H-atom transfer (Chapter 24), phototautomerization (Chapter 28) and the catalytic process in light-driven enzymes (Chapter 36), are also included in this monograph. All the contributions embodied in this proposed book are supported by state-of-the-art experimental and computational results, and the topics cover the wide range of diversity in this field. In my opinion this monograph will serve as a very fundamental tool for understanding excited-state HB and PT processes for researchers in the field of photophysics, photochemistry and photobiology. I strongly recommend the publication of this monograph.

Professor Soo Young Park

School of Materials Science and Engineering, Seoul National University, Korea

Congratulations on your excellent publication. It seems that your book covers all aspects of excited-state H-bonding and H-transfer. This book will draw the attention of scientists in many different disciplines such as the organic, physical, as well as materials chemistry fields.

Professor Swapan K. Saha

Department of Chemistry, University of North Bengal, Darjeeling-734 013, India

Thank you for the mail and the attachments. You have done a great job! Congratulations! The coverage of the proposed book is wide and impressive. The authors are mostly of international standing and the topics covered are up to date and relevant to current interest.

Professor Weiqun Zhou

College of Chemistry and Chemical Engineering, Soochow University, Suzhou 215123, China

The studies on the hydrogen bond have been one of the most important research areas in materials chemistry, chemistry and bioscience. The hydrogen bond has a special significance for biomacromolecules; it is part of the reason why protein and level II, level III and level IV nucleic acid can be stable. The excited-state hydrogen bond structure and dynamics play an important part in many chemical, physical and biological procedures. The fluorescence emission behaviours of organic and biological chromophores are often influenced by the interactions of hydrogen bonds between chromophore molecules and protic solvents or biological surroundings. The ultrafast deactivation processes of the photoexcited molecules and the supramolecular systems are also likely to be easier under the influence of excited-state hydrogen bonding. The hydrogen bond in the excited state and hydrogen transfer are becoming an increasingly important subject in the realm of photochemical and photophysical reactions. The publishing of this book will help us to learn more comprehensively the characteristics of the hydrogen bond and also help us to realize the importance of the hydrogen bond in photochemistry, photobiology and photophysics. We sincerely hope that this book, with systematic description of the hydrogen bond in its excited state and hydrogen transfer, can be published soon.

Professors Sean C. Smith and Hong Zhang

Centre of Computational Molecular Sciences, University of Queensland, Australian Institute of Bioengineering & Nanotechnology, ARC Ctr Funct Nanomat, Brisbane, Qld 4072 Australia

The publication of the book Hydrogen Bonding and Transfer in the Excited State is a timely landmark contribution to the field, drawing together a wide range of theoretical and experimental contributions that collectively provide a comprehensive picture of recent advances in the field. It covers the recent important work of the experts in this field from all over the world and coherently links the theoretical studies with the experimental developments in this important area. The 39 contributing chapters are well written and thematically organized. The book is of high quality and will no doubt become a mandatory part of library and personal collections for institutions and individuals – researchers and students alike – engaged in this fascinating area of molecular science. We look forward to its publication as soon as possible.

Professor Attila Demeter

Institute of Materials and Environmental Chemistry, Chemical Research Centre of Hungarian Academy of Sciences, 1525 Budapest, P.O. Box 17, Hungary

The proposed book Hydrogen Bonding and Transfer in the Excited State, edited by Ke-Li Han and Guang-Jiu Zhao, is a stop-gap issue that may reckon with considerable interest in the field. There is no really well-known monograph on this discipline from the classical books of Pimentel (1960) and Vinogradov (1971), although the subject is widely studied. The 39 studies cover a very wide area, indicating that the understanding of the influence of hydrogen bonds on photoprocesses is crucial almost everywhere. Most expert readers will find half a dozen studies touching upon their close interests; however, the book will be a valuable tool for obtaining knowledge on topics slightly further afield. One rarely has time to collect such scientific studies from journals, and it is certainly valuable to have them gathered together by expert editors.

Professor H. H. Limbach

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195, Berlin

This is a timely book in two volumes and 39 chapters, to which many well-known authors from all over the world have contributed. The systems studied are dyes, water wires, ionic liquids and nanoconfined and self-assembled systems up to biomolecules and large proteins. The appetite of the reader is whetted by chapters covering excited-state phenomena such as vibrational dynamics, acid–base interactions, proton and charge transfers, H-bond-induced conformational switching and molecular recognition, as well as the function of complex proteins. The experimental and theoretical techniques used are adapted to the systems and phenomena studied. It will be an important piece in the canon of books on hydrogen transfer and bonding.

Professor Johannes Kiefer

University Erlangen Nurnberg, LTT, Weichselgarten 8, D-91058 Erlangen, Germany

I very much like the fact that a broad range of aspects is discussed in this book concerning both the analytical methods and the systems under investigation. Therefore, it will be of interest for a large readership in the classical fields of physics and chemistry, but also for rather new areas like life science and biophysics.

Professor Giuseppe Buemi

Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria nr. 6, 95125 Catania, Italy

I have read the summary of the papers enclosed in the new book you have coedited with Prof. Han. Even if I have little experience with excited states, I think that such a book could be very interesting and very useful for collegues working in this field, and so I think the book must be published.

Professor Dipak K. Palit

Radiation & Photochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India

This monograph, presented in two volumes, provides a very timely update on the recent developments in the field of hydrogen-bonding interactions in the excited states of different kinds of molecular system in both homogeneous solutions as well as heterogeneous media, including micelles, vesicles and ionic liquids. As rightly mentioned by the editors in the preface, hydrogen-bonding structures and dynamics in the excited states of molecules play important roles in determining many chemical, physical and biochemical processes. In addition to the most popular fluorescence spectroscopic techniques, recent developments of ultrafast, both linear and nonlinear, time-resolved infrared spectroscopic techniques have provided a great opportunity to understand the microscopic structures and functions in many complex hydrogen-bonded systems. While there are quite a good number of monographs published describing the hydrogen-bonding interactions in the ground state of molecules, to the best of my knowledge there is none to deal with the same aspect exclusively in the excited states of molecules. This book presents an extensive review of the progress of research, both experimental and theoretical, on hydrogen bonding and hydrogen transfer, both intramolecular and intermolecular, in the excited states of a wide variety of molecular systems. This book comprises 39 chapters, most of which are written by experts and provide authoritative overviews of each area. Overall, the editors have fulfilled their primary objective of creating a reference volume valuable to both experts and beginners or students who are engaged in investigation of the dynamics of hydrogen-bonding interactions in the excited states of molecular systems forming hydrogen-bonded complexes. This book will provide an excellent entry to the literature of hydrogen bonding and hydrogen transfers in the excited state.

Professor Andong Xia

The State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, P.R. China

The book entitled Hydrogen Bonding and Transfer in the Excited State, edited by Keli Han and Guangjiu Zhao, is a timely and important work for researchers working on the excited-state hydrogen-bonding structure and dynamics. Reading this book will help the reader understand the basic concepts of complex excited-state hydrogen-bonding processes. There are at least three advantages of this book:

1. The topics covered are extensive and comprehensive. Volume I introduces the structure and dynamics in excited-state hydrogen-bonding systems, and the influences of excited-state hydrogen bonding on photophysical and photochemical processes. Volume II then focuses the attention on the dynamics and control of the excited-state hydrogen proton transfer process. A series of organic chromophores and biomacromolecues in different systems, as well as their inter- and intramolecular hydrogen proton transfer dynamics, are discussed in detail. It has a ‘handbook’ character to some extent, and it is easy to understand the basic concepts of hydrogen bonding for systems specific to researchers.

2. It is very authoritative. The contributed authors are distinguished scholars in this field. Their studies are sufficiently representative of the current overall level in this field.

3. It pays attention to both experimental and theoretical studies. This will be helpful and welcome to experimental researchers seeking theoretical support, and vice versa.

Professor Laszlo Biczok

Hungarian Academy Sciences, Chemistry Research Centre, POB 17, H-1525 Budapest, Hungary

This book provides a unique comprehensive overview of the photoinduced processes of hydrogen-bonded systems. The chapters, written by internationally recognized experts, cover the latest developments and fundamental aspects of this rapidly evolving research field. In view of the ubiquitous nature of hydrogen-bonding and light-initiated processes, this excellent reference book is likely to be of interest to members of a wide scientific community. It serves as a valuable source of information and inspiration for newcomers and experienced researchers alike.

Professor G. Krishnamoorthy

Department of Chemistry, IIT Guwahati, Guwahati 781039, India

Hydrogen bonding is a fundamental phenomenon that plays a key role in various chemical and biological processes. The hydrogen-bonding effects may be altered significantly upon molecular excitation owing to redistribution of electron density in the excited state. This will have a drastic effect on the photochemistry and photophysics of the system. Thus, excited-state hydrogen bonding and hydrogen transfer are very important subjects of study. In this book, recent advances on both experimental and theoretical studies of hydrogen bonding in photochemistry and photophysics are reviewed. The effect of hydrogen bonding on various phenomena, such as proton transfer, charge transfer, isomerization and photodissociation by conventional solvents to complex proteins, clusters and ionic liquids, are discussed. The book will be a useful reference to active researchers and graduate students.

Professor Luca Nardo

University of Insubria, Dept. of Physics and Mathematics & C.N.I.S.M.-C.N.R., U.d.R. Como Via Valleggio 11, 22100 Como, Italy

Concerning the book as a whole, we sincerely think that it has resulted in a really successful editorial project and are proud of having taken part in it. The book is a detailed and comprehensive compendium on all the principal aspects of H-bonding and H-transfer in the excited state, both from the experimental and from the theoretical point of view. The approach of the book sounds intriguingly interdisciplinary. In this regard, we believe that the readership could be quite broad, and that it could be helpful to divide the book into parts/sections, each section collecting chapters on similar topics and being opened by the chapter offering the most complete introduction on both the theory and the experimental techniques eviscerated in the section itself. This should simplify the task of finding specific information within the very wide spectrum of contents. Moreover, the readers would best appreciate the unity and the development of the arguments, and the monographic character of the work. To this purpose, we also suggest that the editors write a short summary/abstract for each section. We see that the order in which the chapters are presented already seems to match these suggestions, and only wish to highlight the opportunity to take up these suggestions.

Professor Oliver Kuhn

Institut für Physik, Universität Rostock, D-18051 Rostock, Germany

As regards the overall impression of the book you have compiled (based on the Table of Contents), I was very excited. You have managed to bring together a very broad range of people essentially covering many of the fascinating subjects of this field. Congratulations!

Professor Pi-Tai Chou

Department of Chemistry, National Taiwan University, Taipei, Taiwan 106

I thank the editors, Dr Ke-Li Han and Dr Guang-Jiu Zhao, for the invitation to contribute a chapter to this new book. The book extensively covers the hot topics of hydrogen bonding and the associated proton (hydrogen) transfer reaction, from theoretical and experimental approaches to the fundamentals to current-interest biological and material applications. I found that this book may be particularly suited to those readers who are at the stage of initiating proton (hydrogen) transfer research and need a broad spectrum of current/previous progress in various aspects. The reader can specifically pick a few chapters for his/her own interest and treat other chapters as key references. This would make the reading more convenient and comfortable. Evidently, the contents of this book are very rich and provide an in-depth discussion of various theories on spectroscopy and dynamics. The reader will be able to discern differences, for example in applications, between similar topics, and, conversely, similarities, for example in theory, between different topics. I thus believe that by reading this book the reader will gain deep and broad insights into hydrogen-bonding phenomena and the associated excited-state proton (hydrogen) transfer reaction and perhaps latent applications in several cutting-edge areas. As for the contemporary research progress in hydrogen-bonding studies, the book is indeed a significant milestone for studying excited-state hydrogen bonding and/or hydrogen transfer reactions.

Professor Ricard Gelabert

Unitat de Quimica Fisica, Departament de Quimica, Edifici Cn Universitat Autonoma de Barcelona, 08193 Bellaterra, Spain

First of all, I have not had access to the contents of the book, either in full or in part, except for the index, the foreword and the abstracts of the different chapters, and as such all I can provide is a general overview or impression of the coverage of the topics related to excited-state proton transfer, as far as my knowledge of the field permits, but not a view on the quality of each of the chapters. The book is made up of 39 chapters, each authored by an author or group of authors active in the general field of hydrogen bonding and hydrogen/proton transfer in excited states. The list of chapters is quite extensive and covers several current topics in ESIPT and hydrogen bonding. In a