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Fundamentals of Photoinduced Electron Transfer by George J. Kaoarnos * VCH Dedicated to the memory of my late brother Preface This book is printed on acid-free paper. @ Library of Congress Cataloging-in-Publication Data Kavamos, George J. Fundamentals of photoinduced electron transfer I by George J. Kavamos. p. cm. Includes index. ISBN 0-89573-751-5 1. Photochemistry. I. Title QD708.2.K38 1993 93-1291 541.3'54~20 CIP O 1993 VCH Publishers, Inc. This work is subject to copyright. All rights reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means and storage in data banks. Registered names, trademarks, etc., used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the United States of America ISBN 0-89573-751-5 VCH Publishers, Inc. Printing History: 1 0 9 8 7 6 5 4 3 2 Published jointly by VCH Publishers, Inc. 220 East 23rd Street New YO&. New York 10010 VCH Verlagsgesellschaft mbH P.O.Box 10 11 61 69451 w e ~ ~ i R d c d Republic of Oamrny VCH Publishers (UK) Ltd. 8 Wellington Court Cambridge CB 1 lfIZ United Kingdom Although numerous review articles on photoinduced electron transfer have appeared in recent years, there is yet no pedagogical text expressly written for undergraduate and graduate students. Fundamentals of Photoinduced Electron Transfer has been written for this readership, and is intended as an introductory text for students of chemistry, biology, physics, and material sciences, as well as readers with a general background in chemistry with an interest in the field. The book is meant as a primary or secondary text in introductory and advanced photochemistry courses at the undergraduate and graduate level. As a self-contained text that includes a brief introduction to the principles of photochemistry, this book can also be used in a course exclusively devoted to photoinduced electron transfer, or it can be used as a supplementary source in chemistry and biology courses for advanced undergraduates or beginning graduate students. Fundamentals of Photoinduced Electron Transfer requires, at the minimum, 2 or 3 years of college chemistry (general, organic, and physical). Accordingly, the material is within the grasp of junior or senior undergraduates with no prior knowledge of photochemistry or electrochemistry. The author has included material that should appeal to chemists, physicists, and biologists who may want to familiarize themselves with this vital subject. The book is not intended as a comprehensive review. For those requiring additional and specialized information, the review articles listed at the end of each chapter should suffice. In writing on such a rapidly expanding field, it was virtually impossible to include all of the excellent research that has been done. Consequently, it was found necessary to exclude several lines of research. An effort, however, was made to limit these omissions. The material in the first few chapters is presented at a level to allow the student to become comfortable with p e subsequent subject matter. The first chapter vi FUNDAMENTALS OF PHOTOINDUCED ELECTRON TRANSFER introduces the reader to the basic principles and terminology of photochemistry. Chapter 1 also introduces the student to the Weller equation and the role of energetics. In Chapter 2, the properties of ion pairs and exciplexes are discussed as well as experimental procedures to study them. Chapter 3 covers photoinduced electron-transfer reactions of organic substrates; Chapter 4 deals with intramolecular and supramolecular photoinduced electron transfer. A number of topics are covered in Chapt