A Born-Oppenheimer approach to adiabatic electrochemical charge transfer processes

An approach for the construction of the Hamiltonians and free energy surfac es for adiabatic electrochemical reactions accompanied by a considerable re organization of the intramolecular structure is presented. For one-electron processes it reproduces the results of Koper and Voth (Chem. Phys. Lett. 2 82 (1998) 100) without an a priori introduction of a switching function tra nsforming the bonding molecular potential into an antibonding one. The pres ent approach is extended to two-electron processes, which are of importance for the dissociative adsorption and electrocatalysis. (C) 2000 Elsevier Sc ience S.A. All rights reserved.