Cl electrosorption on Ag(100): Lateral interactions and electrosorption valency from comparison of Monte Carlo simulations with chronocoulometry experiments

TL;DR

This study uses Monte Carlo simulations and experimental data to analyze chloride electrosorption on silver surfaces, revealing how lateral interactions and electrosorption valency depend on coverage and electrostatic effects.

Contribution

It introduces a self-consistent electrostatic model linking coverage-dependent lateral interactions with electrosorption valency for Cl on Ag(100).

Findings

Coverage-dependent lateral interaction energy phi_nnn is established.

Electrosorption valency gamma varies with coverage.

Monte Carlo simulations fit well with chronocoulometry data.

Abstract

We present Monte Carlo Simulations using an equilibrium lattice-gas model for the electrosorption of Cl on Ag(100) single-crystal surfaces. Fitting the simulated isotherms to chronocoulometry experiments, we extract parameters such as the electrosorption valency gamma and the next-nearest-neighbor lateral interaction energy phi_nnn. Both coverage-dependent and coverage independent gamma were previously studied assuming a constant phi_nnn [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 phi_nnn is developed, and a relationship between phi_nnn and gamma is investigated for Cl on Ag(100).