Mechanisms of Fast Reactions in Solution

by E. F. Caldin

Overview

This book deals with the contribution of fast reaction techniques to our understanding of events on the molecular scale during chemical reactions. It covers the advances resulting from the combination of chemical kinetic and spectroscopic methods and highlights the information to be obtained from ultrafast processes lasting a few picoseconds or less. Computerised molecular dynamics calculations are shown to be an additional important tool. These methods have transformed the extent of detail of knowledge it is now possible to obtain of individual reaction mechanisms. The book contains sections on: the rates of diffusion-controlled reactions, the mathematical theory of diffusion and diffusion-controlled reaction rates, flash-photolysis techniques, initiation by high-energy radiation: plus radiolysis, fluorescence quenching and energy-transfer from excited molecules, ultrafast processes: sub-picosecond and femtosecond techniques, proton-transfer and group-transfer reactions in solution: Marcus theory (I) and electron-transfer reactions: Marcus theory (II).

Product Details

ISBN-13:	9781586031039
Publisher:	IOS Press, Incorporated
Publication date:	11/28/2001
Pages:	329
Product dimensions:	6.40(w) x 9.70(h) x 1.00(d)

Table of Contents

	Preface	v
	Foreword	vii
	Acknowledgements	viii
	Prologue	xi
Part 1
Chapter 1.	Introduction: Origins, Methods, Mechanisms, Rate Constants
1.1.	Introduction	3
1.2.	The structure of this book	10
1.3.	Theory of rate constants for diffusion-controlled reactions	12
	References	18
Chapter 2.	The Rates of Diffusion-Controlled Reactions
2.1.	Introduction	21
2.2.	Application of the diffusion law to rates of encounter and of chemical reaction: the Smoluchowski equation	21
2.3.	A molecular model for translational diffusion and diffusion-influenced rates of reaction: random-walk theory	31
2.4.	Encounter in solution: the solvent 'cage'	33
2.5.	The course of an encounter	36
2.6.	Alternative theoretical approaches: refinement of theory	45
	References	48
Chapter 3.	The Mathematical Theory of Diffusion and Diffusion-Controlled Reaction Rates
3.1.	Introduction	51
3.2.	Theory of rates of diffusion, in terms of concentration gradients	54
3.3.	Calculation of diffusion-controlled rate constant	59
3.4.	Diffusion coefficients: theory and experiment	65
	References	79
Chapter 4.	Flash Photolysis Techniques
4.1.	Introduction	81
4.2.	Experimental flash techniques	85
4.3.	Some applications of flash techniques	98
	References	115
Chapter 5.	Initiation by High-Energy Radiation: Pulse Radiolysis
5.1.	Introduction	119
5.2.	Experimental techniques	122
5.3.	Some applications of pulse radiolysis	125
	References	136
Part 2
Chapter 6.	Fluorescence Quenching and Energy-Transfer from Excited Molecules
6.1.	General principles	141
6.2.	Theory of fluorescence quenching	142
6.3.	Experimental investigation of fluorescence quenching	151
6.4.	Kinetic and mechanistic applications of fluorescence measurements	156
6.5.	Physical mechanisms for non-radiative energy transfer between molecules	167
	References	187
Chapter 7.	Ultrafast Processes: Sub-Picosecond and Femtosecond Techniques
7.1.	Introduction	191
7.2.	Femtosecond studies of the entire reaction path	192
7.3.	Some systems studied by sub-picosecond and femtosecond techniques	197
	References	221
Part 3
Chapter 8.	Proton-Transfer and Group-Transfer Reactons in Solution: Marcus Theory (I)
8.1.	Marcus theory. Introduction	227
8.2.	Application of Marcus theory to proton-transfer reactions in solution	228
8.3.	Application of Marcus theory to group transfer	256
8.4.	Refinements and extensions of the Marcus treatment	261
	References	261
Chapter 9.	Electron-Transfer Reactions: Marcus Theory (II)
9.1.	Introduction	265
I.	Electron-transfer in outer-sphere reactions of metal ions	266
9.2.292
II.	Electron-transfer reactions in organic systems	292
9.3.	Tailpiece: a brief re-capitulation	317
	References	318
	Epilogue	323
	List of symbols used frequently in the Marcus theory of reactions	325
	Subject Index	327

Editorial Reviews

Published a few years after the author's death, this volume is a sequel to his 1964 book, Fast Reactions in Solution; the material is entirely new, extending investigation beyond now well-established fast-reaction techniques to consider their contribution to understanding events on the molecular scale. After an introductory chapter on origins, methods, mechanisms, and rate constants, coverage includes the rates of diffusion-controlled reactions, mathematical theory of diffusion, flash photolysis techniques, fluorescence quenching, Marcus theory involving proton-transfer and group-transfer reactions in solutions, and electron-transfer reactions. Annotation c. Book News, Inc., Portland, OR