Nonlocal Electrostatic Effects on Electron-Transfer Activation Energies: SomeConsequences for and Comparisons with Electrochemical and Homogeneous-Phase Kinetics

摘要

The combined role of field penetration into the metal electrode and solventspatial correlations (nonlocal electrostatics) upon the outer-shell free energy of activation for electrochemical exchange reactions as described by a recent treatment are explored in relation to the activation free energy of homogeneous self-exchange processes by means of illustrative numerical calculations, and by comparisons with experimentally derived barriers. The latter are obtained from solvent-dependent kinetic data for cobaltocenium-colbaltocene electrochemical exchange and homogeneous self exchange, along with optical electron-transfer energies for biferrocenylacetylene cation (BFA+). Keywords: Nonlocal electrostatic effects, Electron-transfer activation energies, Electrochemical and homogeneous-phase kinetics, Reprints. (jes)