Molecular orbital approach to the study of electrochemical interfaces

Abstract

The capabilities and limitations of a semiempirical electrode valence band shifting model for studying the potential dependence of chem. at electrode surfaces are discussed. The importance of perturbation theory concepts to understanding the results of the calcns. is stressed. The atom superposition and electron delocalization MO (ASED-MO) theory, which has found application in this approach, is outlined. Examples discussed include C.tplbond.O, C.tplbond.C, O-H and C-H potential dependent bond activation over various metals and oxides. The approach shows promise for understanding and predicting the mechanisms of electrocatalysis involving species adsorbed on electrode surfaces in terms of the potential dependence of orbital donor and acceptor interactions.