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INTRODUCTION TO MARCUS THEORY OF ELECTRONTRANSFER REACTIONS
Copyright © 2020 by World Scientific Publishing Co. Pte. Ltd.
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A Liliana e Valentina
Foreword
The author of this volume, Professor Francesco Di Giacomo, a member of the engineering faculty of the University of Rome, was also, some 40+ years ago, a visitor in my group, at that time at the University of Illinois. More recently he set himself the daunting task of learning about the theory of electron transfer reactions, with a background that included some research on the quantum mechanics of potential energy surfaces but none on key aspects of electron transfer theory—the dynamical features of quantum and classical theory, the statistical mechanics of chemical reactions, and features such as nonequilibrium dielectric polarization. They form the core of the theory and its applications. To this end he supplemented his study of my electron transfer articles by many hour-long question and answer sessions that we held, largely via Skype. Francesco comes with a delightful background rich in cultural and scientific history, especially of the ancient Greek and Roman periods. It added another side to our many discussions, an aspect that does not come out in this book but is seen in articles he has published elsewhere. Our discussions on the electron transfer articles involved many fine points of the theory and of its history, points that are described in this book. With his background Professor Di Giacomo’s scientific questions have a fresh and novel point of view that was both interesting and challenging. It adds to the novelty of the book. Hopefully the readers will find it equally so, in their study of the theory, of its history and in exploring the many distinct concepts that electron transfer processes present.
Rudolph A. Marcus
California Institute of Technology, March 2019
Preface
To learn about the theory of electron transfer reactions, I have followed, with David Mermin, “the time honored method of writing a book,” systematically interviewing the most famous scientist in the field, Professor Rudolph A. Marcus for whom I had the honor of being Research Associate at the University of Illinois at Urbana-Champaign. Most of the interviews took place through Skype connections between Rome and Pasadena, but some occurred at Caltech, and the first one happened on board of a Southwestern Airlines flight between Oakland and Burbank airports, while we were coming back to Pasadena from San Francisco. There, in October 2006, a Special Symposium of the American Chemical Society had been held to celebrate the 50th year from the publication of Marcus’ first paper on the theory, back in 1956.
I have written this book mainly to teach myself and I believe it may be useful for other beginners. The book aims at introducing the Marcus Theory of Electron Transfer Reactions from reading of Marcus’ papers. Only excerpts from each paper are cited which are important at first reading. The layout is, when possible, like that of lecture notes, more “open” and reader friendly than the layout of the original paper. In the text simple notes of the author are presented which may be of help to the student or the beginner. At the end of each paper are Marcus’ Notes with his comments and remarks, an accompaniment interesting to students and scholars in the field of electron transfer reactions. Finally, during the transcription of excerpts from the original papers, typos and small errata have been corrected.
In this book, 57 papers on the Marcus theory of electron transfer are considered, spanning the 30 years from 1956 to 1986. After an introductory chapter by the author, Marcus’ papers are described, either closely following their content or summarizing and abridging the original text. At the end of the first eight chapters, there are lists of references, in the subsequent three chapters only references to Marcus’ papers are reported in the form MN where M stands for Marcus and N is the order number in the official list of Marcus’ publications. The last two chapters report oral interviews with Marcus with notes on his papers.
I shall consider this work successful if it will help the reader to better appreciate the Marcus theory of electron transfer from its primary source, Marcus’ papers. A following book will contain oral interviews with Marcus with notes on his papers ranging from 1987 onward, up to the most recent ones.
F. Di Giacomo
Roma 2019
Scheme of the Book, Figures, Notes, and Abbreviations
The book has the format of a textbook but is not a textbook. It is a collection of excerpts from many of Marcus’ papers with explanatory notes from the author and, much more importantly, with notes by Marcus on his papers.
The book may of course be read from cover to cover as a textbook, but it is more in general intended for readers interested in particular papers of Marcus to get an introduction to them and to read the related Marcus’ notes. It is an anthology of Marcus’ papers. Passages from the papers are reported in the book as they appear in the original publication. It so happens then that a topic may be treated in different papers in a similar way so that in the book there are sections which may be partly repetitive because Marcus normally treats the same topic in slightly different ways in his papers, moreover the sections are reported with figures from
