Radiationless Transitions

1st Edition - January 1, 1980
Editor: Sheng Lin
Language: English
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 5 0 2 7 - 9

Radiationless Transitions is a critical discussion of research studies on the theory and experiments in radiationless transitions. This book is composed of nine chapters, and… Read more

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Radiationless Transitions is a critical discussion of research studies on the theory and experiments in radiationless transitions. This book is composed of nine chapters, and begins with discussions on the theory and experiment of photophysical processes of single vibronic levels and/or single rovibronic levels. The subsequent chapters deal with the spectroscopic investigations of intramolecular vibrational relaxation; the dynamics of molecular excitation by light; and the photophysical processes of small molecules in condensed phase. The discussions then shift to the high pressure effects on molecular luminescence and the internal conversion involving localized excitations, presenting one qualitative and one quantitative example, as well as the intersystem crossing with localized excitations. A chapter explores the energy transfer processes that occur after a molecule in solution is excited by light, with an emphasis on solid solutions in which the large amplitude molecular motion is largely quenched. This chapter also looks into the liquid solutions in which the molecules can translate and rotate under the influence of fluctuating forces from the liquid. The concluding chapter focuses on ultrafast processes. Researchers in the fields of physics, chemistry, and biology will benefit from this book.

List of Contributors

Preface

1 Experimental Measurement of Electronic Relaxation of Isolated Small Polyatomic Molecules from Selected States

I. Introduction

II. Theoretical Background

III. Experimental Studies on Small Triatomic and Tetra-Atomic Molecules

IV. Experimental Studies on Six-Atom and Larger Molecules

References

2 Rotational Fine Structure in Radiationless Transitions

I. Introduction

II. The Excited State Rotational Distribution

III. Isolated Molecule Conditions and Collisional Energy Redistribution

IV. Experimental Evidence for a Rotational Effect in Nonradiative Processes

V. Rotational State Matrix Elements and Selection Rules

VI. The Rate Constant for Nonradiative Transitions

VII. Energy Matching in Isolated Molecules

VIII. Vibrational Effects in Nonradiative Transitions

IX. The Decay of a Multilevel System

X. Model Calculations

XI. Conclusion

References

3 On Rotational Effects in Radiationless Processes in Polyatomic Molecules

I. Introduction

II. The Diatomic Molecule Case

III. The Polyatomic Molecule Case

IV. Modeling the Effect of Intermanifold Coriolis Coupling

V. Rotational Effects in Spin-Orbit Coupling

VI. Angular Momentum Conservation in Polyatomic Fragmentation Reactions

VII. Concluding Remarks

Appendix: Tensor and Angular Momentum Algebra

References

4 Vibrational Relaxation of Isolated Molecules

I. Introduction

II. Theoretical Models

III. Experimental Studies

IV Concluding Remarks

Appendix

References

5 Dynamic Aspects of Molecular Excitation by Light

I. Introduction

II. Basic Premises

III. Selective Excitation

IV Spectral Analysis of Coupling Schemes

V. Summary: Perspectives and Predictions

References

6 Spectroscopic and Time Resolved Studies of Small Molecule Relaxation in the Condensed Phase

I. Introduction

II. Spectra and the Physical Interpretation of Molecular Lineshapes

III. Large Amplitude Vibrational and Electronic Motion

IV. Electronic Solvation and Adiabatic Potential Changes

V. Radiationless Transitions Observed by Polarization and Fluorescence Line Narrowing

VI. Direct Vibrational Relaxation

VII. Vibrational Relaxation through Real Intermediate States

VIII. Atomic Relaxation

IX. Vibrational Relaxation in Triatomics

X. Vibrational Energy Transfer

XI. Observation of Missing States

References

7 High Pressure Studies of Luminescence Efficiency

I. Introduction

II. Internal Conversion

III. Intersystem Crossing

IV. Delocalized Excitation—Doped ZnS

V. Energy Transfer

VI. Viscosity Effects on Luminescence Efficiency

References

8 Relaxation of Electronically Excited Molecular States in Condensed Media

I. Introduction

II. Dynamical Effects in Condensed Phases

III. Experimental Methods

IV. Vibrational Relaxation in Optically Excited States

V. Electronic Relaxation

VI. Summary and Prospects

References

9 Some Considerations of Theory and Experiment in Ultrafast Processes

I. Introduction

II. Time Evolution of a Relaxing System

III. Spectral Line Shapes

IV. Vibrational Relaxation

V. Migration of Particles

VI. Memory Function

Appendix I

Appendix II

References

Index