CONTEMPORARY QUANTUM-CHEMICAL MODELING OF ELECTRIFIED INTERFACES

Attempts of describing metal/solution interfaces on the basis of clust er model and quantum chemical methods of different levels, made during the past decade, are surveyed and critically discussed. Even relative ly small clusters modelling of a metal surface are shown to be an effe ctive implement to handle fundamental problems of the double layer the ory. Liophilicity of metals, dissociative water chemisorption, adsorpt ion of hydrated ions and the contribution of a metal electrode to the interfacial capacity are topics of primary attention in this paper. In order to elaborate a new molecular model for a charged electrode surf ace, we consider in detail specific problems of the quantum chemical a pproaches and possible ways to surmount these. To supplement the pictu re of the state-of-the-art in the area of microscopical modelling unde r consideration, we report some original results concerning the study of hydrophilicity of low-index silver faces. The interplay between tra ditional electrochemical model concepts and ''quantum chemical'' langu age is illustrated by a great deal of both db initio and semi-empirica l calculations. Copyright (C) 1996 Elsevier Science Ltd