Microscopic modelling of the reduction of a Zn(II) aqua-complex on metal electrodes

The mechanism of the Zn(II) reduction from acid aqueous solution at a metal electrode surface has been elucidated at a microscopic level. The Anderson-Newns model was employed in order to construct the adiabatic potential energy surfaces along the solvent coordinate for several reactions as a function of the electrode-reactant distance and the overpotential. A quantum chemical approach was employed to treat the coupling of the reactant to the metal electrode within a cluster model. The reduction of a [Zn(H2O)(6)](2+) complex was found to proceed in the adiabatic regime, the transfer of the first electron being rate-determining. Main attention is focused on effects of a qualitative nature, which are discussed in the light of available experimental data. The electrode charge excess and distance of maximal approach were found to affect significantly the Frank-Condon barriers of the reaction. An experimentally observed dependence of the rate constant of Zn(II) reduction upon the electrode material has been interpreted. (C) 2004 Elsevier B.V. All rights reserved.