electron transfer reactions in chemistry. theory and experiment

Electron transfer reactions in chemistry. Theory and experiment Rudolph A. Marcus Rev. Mod. Phys. 65, 599 – Published 1 July 1993

Electron transfers are frequently rather fast, compared with many reactions which undergo, instead, a breaking of chemical bonds and a forming of new ones. Accordingly, the study of a large body of fast electron transfer reactions became accessible with the introduc-tion of this instrumentation.

Extremely fruitful in many fields of chemistry, the theory Marcus developed in the fifties and sixties describes thermal electron transfer reactions. In his Nobel lecture, Marcus gives a short history of the development of the theory, mentions some of the predictions from it such as the occurrence of an inverted region for strongly exothermic ...

Since the late 1940s, the field of electron transfer processes has grown enormously in chemistry, electrochemistry, and biology. The development of the field, experimentally and theoretically, as well as its relation to the study of the other kinds of chemical reactions, presents an intriguing history in which many threads have been brought ...

The mechanisms and the applications in organic synthesis, materials, supramolecular, and polymer synthesis of most organic reactions mediated by single electron transfer are discussed, even though both biology and radical chemistry rely extensively on one-electron transfer processes.

One of the active areas in reaction kinetics during the post-war years has been that of electron-transfer reactions. These reactions constitute one type of oxidation-reduction process and include both chemical and electrochemical systems.

Some of the theories that have been used to rationalize the dynamics and temperature dependence of the electron-transfer reactions, including Marcus theory, coupling to quantized vibrational modes and density-matrix treatments are discussed.

This theory, an elastic molecular transfer theory, provides a framework for a multistate model and includes the probe used in single-molecule imaging and magnetic manipulation experiments.

Electron transfers are frequently rather fast, com- pared with many reactions which undergo, instead, a breaking of chemical bonds and a forming of new ones. Accordingly, the study of a large body of fast electron transfer reactions became accessible with the introduction of this instrumentation.

The early experiments in the electron transfer field were on “isotopic exchange reactions” (self-exchange reactions) and, later, “cross reactions.” These experiments reflected two principal influences.