REORGANIZATION ENERGY FOR ELECTRON-TRANSFER AT FILM-MODIFIED ELECTRODE SURFACES - A DIELECTRIC CONTINUUM MODEL

Electron transfer between an electrode and a redox couple separated fr om the electrode by an organic film is analyzed using a local dielectr ic continuum model. The solvent reorganization energy (E(s)) is calcul ated as a function of the cavity radius of the redox group, the thickn ess of the organic film, and the static and optical dielectric constan ts of the solvent, the organic film, and the electrode. Comparison is made between results for E(s) based on alternative formulations in ter ms of electric field vectors, and significant differences are found, b oth quantitative and qualitative.