Electron transfer theory and its inception

Abstract

It is a pleasure to introduce this issue on electron transfer processes. The field has developed greatly and in many different directions not envisioned in the late 1940s. The modern electron transfer era began at that time in the form of studies on the simplest class of reactions in all of chemistry, isotopic exchange reactions of the electron transfer type. In their simplest form no chemical bonds are broken or formed, only an electron is transferred from one reactant to the other. I remember how surprised and excited I was reading in 1955 a paper by Bill Libby (W. F. Libby, J. Phys. Chem., 1952, 56, 893), written several years earlier, explaining why some of these reactions were slow and others fast. In his explanation he used the Franck–Condon principle to interpret the results: he noted that when an electron "jumped" from one reactant to the other the slow moving nuclei changed neither their positions nor their momenta during the jump, and what the consequences were. I was especially excited, since that principle had originally been introduced to explain molecular spectra rather than chemical reaction rates. But perhaps at this point I should say a few words on how I came into theoretical chemistry as a practitioner just a few years earlier.

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