On the theory of electron-transfer processes in aqueous solutions

Abstract

It has been realized for some time that simple electron-transfer processes play an important part in the mechanism of many oxidation-reduction reactions in solution. An attempt has been made to give a quantum-mechanical interpretation of these processes on the basis of the earlier theories of electron transfer in the gaseous state (Landau 1932; Bates & Massey 1943). The present treatment for solutions takes into account the role of the solvent, with particular reference to the operation of the Franck—Condon principle and it also leads to some definite picture of the transition state for the electron transfer process. A number of examples are discussed, including electron transfer between like ions of different valency and also reactions involving complex ions, e.g. metal porphyrins, the reactions of which are of importance in certain biochemical processes. It appears that the application of certain theoretical principles leads to a satisfactory understanding of electron-transfer processes in solution from a qualitative and, in some cases, also from a semi-quantitative point of view.