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ESR of Reacting Radicals

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Abstract

This paper represents a review of my research that was presented upon receiving the 2012 Zavoisky Award given by the Zavoisky Physical-Technical Institute in Kazan, Tatarstan, Russia. It is my belief that my early experiences gave an important background for experimental research and success in the area of ESR (electron spin resonance). I will describe some of these. In addition, I will give some of my educational experience that displayed how random chance was also important as to what research area I adopted. Much of my research has been with ESR of radicals produced by ionizing radiation and some of the more important observations are described. Among them is the initial discovery of chemically induced dynamic electron polarization (CIDEP). Also mentioned are a treatment of second-order hyperfine splittings and a number of issues regarding radical structure. This work also contributed to spectrometer design for time-resolved experiments. Modified Bloch equations were developed to describe the ESR time dependence. A number of observations on the hydrated electron, e −aq , are described, including the finding of an “inverse” CIDEP when e −aq is present with certain counter radicals. Several more recent studies finally explained this behavior. Two topics not used in the presentation are also included: a determination of the relaxation time of e −aq and a determination of relative radical yields in pulse radiolysis. Finally, two other applications of microwave absorption are described, including a new method for determining the dipole moments of photo-excited molecules.

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Acknowledgments

First, I must express my deepest thanks to Prof. Kev Salikov and the committee that chose to present me with the 2012 Zavoisky Award. To be included in the list of past recipients is a great honor. I also thank the Zavoisky Physical-Technical Institute, Kazan Federal University, Government of the Republic of Tatarstan, and Springer for support of this award. Direct financial support from Springer and the Government of the Republic of Tatarstan is also gratefully acknowledged. I wish to acknowledge the contributions to my experience and research from advisors, associates, students, and technical staff. In the first category are my senior thesis advisor at University of Massachusetts, Richard S. Stein, my PhD advisor John S. Waugh at MIT, and Harden M. McConnell at Caltech for my postdoctoral year. They provided inspiration, guidance, and advice. There have been PhD and MS students, and associates at Mellon Institute, Carnegie-Mellon University, and at Notre Dame. They have contributed in a very important fashion to my work. Names have been included where they have made major contributions to topics that I have presented. I do not intend to imply that those not mentioned did not also contribute significantly. I have tried to distinguish cases where the original idea was mine (second-order splittings, various spectrometer developments, and time-resolved microwave dielectric absorption, for example). However, further development of those projects usually represented group efforts with contributions from all. Finally, I wish to thank Robert H. Schuler and his support as Institute Director for a large number of years as well as for direct interaction in a number of collaborations. Subsequent directors are also to be thanked including the most recent, Ian Carmichael. It is notable that I have received support (through the Radiation Laboratories) from the same agency, now the US Department of Energy, Basic Energy Sciences, and its predecessors for all of 40 years. I am greatly indebted to them for such support. There has always been a fine line between basic research for the sake of new knowledge and that applied to the specific interests of such agencies. Fortunately, I have been able to pursue my findings without too many restrictions. This question is one of much current debate and I believe research for knowledge sake must be defended vigorously. I believe that many important discoveries have originated in the course of other specific research. The discovery of CIDEP is one obvious example here. This aspect of research we all recognize and it was well described by Joseph Priestley over 239 years ago. “In completing one discovery we never fail to get an imperfect knowledge of others, of which we could have no idea before; so that we cannot solve one doubt without creating several new ones” [41].

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    Richard W. Fessenden

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Fessenden, R.W. ESR of Reacting Radicals. Appl Magn Reson 45, 483–503 (2014). https://doi.org/10.1007/s00723-014-0535-5

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