Hydrogen Bonding and Transfer in the Excited State E-Book

Ke-Li Han

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 2183

Veröffentlichungsjahr: 2011

Beschreibung

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.

Leseprobe

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

This edition first published 2011

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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-LiHan 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-JiuZhao 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