Determination of Reaction and Reorganization Free Energies of Electron Transfer Reactions under Restricted Geometry Conditions

Abstract

In this paper, different methods of obtaining the two parameters controlling the rate of electron transfer processes (reaction and reorganization free energies, Λ and Δ G0’, respectively) under restricted geometry conditions are considered. The main difficulty of accomplishing this comes from lack of knowledge of the properties in the interfacial region, where the reaction occurs. A general method has been presented and illustrated with the study of intermolecular processes in micelles. This method is optimized when the free energies for (at least) the three reactions required are quite different. For excited state electron transfer, the general approach is based on the appearance of the so-called Marcus inverted region: at the starting point of this region the value of Δ G0’ gives the value of Λ directly. These reaction free energies also present some uncertainties because in their calculation it is necessary to know the value of the local dielectric constant. Finally, it should be mentioned that some authors have suggested that the treatments for electron transfer reactions could not be applicable under restricted conditions. However, experiments do seem to show the applicability of the Marcus-Hush treatment under these conditions.