Development of open-boundary cluster model approach for electrochemical systems and its application to Ag+ adsorption on Au(111) and Ag(111) electrodes

Abstract

We present a theoretical method to investigate electrochemical processes on the basis of a finite-temperature density functional theory (FT-DFT) approach combined with our recently developed open-boundary cluster model (OCM). A semi-infinite electrode is well mimicked by a finite-sized simple cluster with an open quantum boundary condition rationalized by OCM. An equilibrium state between adsorbates and an electrode is described by the grand canonical formulation of FT-DFT. These implements allow us to calculate electronic properties of an adsorbate and electrode system at a constant chemical potential μ, i.e., electrode potential. A solvation effect is approximated by a conductor-like polarized continuum model. The method is applied to the electrochemical processes of Ag(+) adsorption on Au(111) and Ag(111). The present constant μ approach has proved essential to electrochemical systems, demonstrating that the method qualitatively reproduces the experimental evidence that Ag(+) adsorbs more on the Au electrode than the Ag one, while the conventional quantum chemistry approach with a constant number of electrons incorrectly gives exactly the opposite result.