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

Electron transfer between an electrode and a redox couple separated from the electrode by an organic film is analyzed using a local dielectric continuum model. The solvent reorganization energy (E(s)) is calculated as a function of the cavity radius of the redox group, the thickness of the organic film, and the static and optical dielectric constants of the solvent, the organic film, and the electrode. Comparison is made between results for E(s) based on alternative formulations in terms of electric field vectors, and significant differences are found, both quantitative and qualitative.