Computational Lattice-Gas Modeling of the Electrosorption of Small Molecules and Ions

We present two recent applications of lattice-gas modeling techniques to electrochemical adsorption on catalytically active metal substrates: urea on Pt(100) and (bi)sulfate on Rh(111). Both involve the specific adsorption of small molecules or ions on well-characterized single-crystal electrodes, and they provide a particularly good fit between the adsorbate geometry and the substrate structure. The close geometric fit facilitates the formation of ordered submonolayer adsorbate phases in a range of electrode potential positive of the range in which an adsorbed monolayer of hydrogen is stable. In both systems the ordered-phase region is separated from the adsorbed- hydrogen region by a phase transition, signified in cyclic voltammograms by a sharp current peak. Based on data from {\it in situ\/} radiochemical surface concentration measurements, cyclic voltammetry, and scanning tunneling micro- scopy, and {\it ex situ\/} Auger electron spectroscopy and low-energy electron diffraction, we have developed specific lattice-gas models for the two systems. These models were studied by group-theoretical ground-state calcu- lations and numerical Monte Carlo simulations, and effective lattice-gas inter- action parameters were determined so as to provide agreement with experiments.Comment: 17 pp. uuencoded postscript, FSU-SCRI-94C-9

Underpotential deposition of Cu on Au(111) in sulfate-containing electrolytes: a theoretical and experimental study

We study the underpotential deposition of Cu on single-crystal Au(111) electrodes in sulfate-containing electrolytes by a combination of computational statistical-mechanics based lattice-gas modeling and experiments. The experimental methods are in situ cyclic voltammetry and coulometry and ex situ Auger electron spectroscopy and low-energy electron diffraction. The experimentally obtained voltammetric current and charge densities and adsorbate coverages are compared with the predictions of a two-component lattice-gas model for the coadsorption of Cu and sulfate. This model includes effective, lateral interactions out to fourth-nearest neighbors. Using group-theoretical ground-state calculations and Monte Carlo simulations, we estimate effective electrovalences and lateral adsorbate--adsorbate interactions so as to obtain overall agreement with experiments, including both our own and those of other groups. In agreement with earlier work, we find a mixed R3xR3 phase consisting of 2/3 monolayer Cu and 1/3 monolayer sulfate at intermediate electrode potentials, delimited by phase transitions at both higher and lower potentials. Our approach provides estimates of the effective electrovalences and lateral interaction energies, which cannot yet be calculated by first-principles methods.Comment: 36 pages, 14 Postscript figures are in uufiles for