Cl electrosorption on Ag(1 0 0): Lateral interactions and electrosorption valency from comparison of Monte Carlo simulations with chronocoulometry experiments

We present Monte Carlo simulations using an equilibrium lattice-gas model for the electrosorption of Cl on Ag(1 0 0) single-crystal surfaces. Fitting the simulated isotherms to chronocoulometry experiments, we extract parameters such as the electrosorption valency γγ and the next-nearest-neighbor lateral interaction energy ϕnnnϕnnn. Both coverage-dependent and coverage-independent γγ were previously studied, assuming a constant ϕnnnϕnnn [I. Abou Hamad, Th. Wandlowski, G. Brown, P.A. Rikvold, J. Electroanal. Chem. 554–555 (2003) 211]. Here, a self-consistent, entirely electrostatic picture of the lateral interactions with a coverage-dependent ϕnnnϕnnn is developed, and a relationship between ϕnnnϕnnn and γγ is investigated for Cl on Ag(1 0 0).