ABSTRACT
Rate constants for electron transfer between weakly coupled donor (D) and acceptor (A) sites are formulated theoretically in the context of a broad kinetic framework capable of accounting for homogeneous processes and interfacial processes involving metal electrodes. Particular emphasis is placed on two crucial kinetic parameters, the solvent reorganization energy (Es) and the D/A coupling element (HDA ). The results of model calculations are described, which show how the behavior of these quantities may be evaluated and analyzed theoretically and then successfully related to results inferred from electrochemical kinetic measurements. The theory underlying the calculations allows the formulation of compact models of predictive utility that are valuable in suggesting critical new experimental tests of theory.
