Ab Initio Simulation of Metal Cluster Surrounded by Electrolyte

Abstract

An effective and computationally economical scheme, which unifies density functional description of a metal electronic structure and the classical molecular dynamics description of an electrolyte in contact with the metal, is described. The density functional part of the scheme comprises Car‐Parinello and related formalisms. This scheme allows the extension to longer time scale of the simulation of metal‐electrolyte interface while keeping fairly good accuracy in the prediction of the metal electronic structure. The numerical scheme is implemented in the relatively simple model of a metal cluster surrounded by an electrolyte. The elementary event of an atom leaving a metal surface as an ion stabilized by solvent molecules has been studied. In particular the potential of mean force of the ion as it dissolves was evaluated. The evolution of the solvation shell of the ion as it leaves the surface is calculated as a further example. © 2000 The Electrochemical Society. All rights reserved.