Electron transfer reactions at metal electrodes: Influence of work function on free energy of activation and exchange current density

The dependence of the free energy of activation on the work function of electrodes, solvation energies, and surface potentials of the reactant species pertaining to electron transfer reactions at metal/solution interfaces is derived using thermodynamic considerations. The standard exchange current density is calculated for Fe3++e <----> Fe2+ at different metal electrodes and compared with experimental data as well as molecular dynamics simulations. (C) 2001 American Institute of Physics.