Parameter Estimation by Density Functional Theory for a Lattice-gas Model of Br and Cl Chemisorption on Ag(100)

TL;DR

This study uses density functional theory to parameterize a lattice-gas model for Br and Cl chemisorption on Ag(100), revealing the nature of lateral interactions and providing insights into adsorption energetics.

Contribution

The paper introduces a DFT-based method to estimate parameters for a lattice-gas model of halogen chemisorption on silver surfaces, linking microscopic calculations with macroscopic adsorption behavior.

Findings

Long-range dipole-dipole interactions are significant for Br.

Short-range attractions are present for Cl.

Results align with previous Monte Carlo simulation estimates.

Abstract

We study Bromine and Chlorine chemisorption on a Ag(100) surface, using a lattice-gas model and the quantum-mechanical Density Functional Theory (DFT) method. In this model the Br and Cl ions adsorb at the fourfold hollow sites of the Ag(100) surface, which can be represented by a square lattice of adsorption sites. Five different coverages were used for each kind of adsorbate. For each adsorbate and coverage, we obtained the minimum-energy configuration, its energy, and its charge distribution. From these data we calculated dipole moments, lateral interaction energies, and binding energies. Our results show that for Br the lateral interactions obtained by fitting to the adsorption energies obtained from the DFT calculation are consistent with long-range dipole-dipole lateral interactions obtained using the dipole moments calculated from the DFT charge distribution. For Cl we found that, while the long-range dipole-dipole lateral interactions are important, short-range attractive interactions are also present. Our results are overall consistent with parameter estimates previously obtained by fitting room-temperature Monte Carlo simulations to electrochemical adsorption isotherms [I.\ Abou Hamad et al., J.\ Electroanal. Chem.\ 554 (2003), 211; Electrochim.\ Acta 50 (2005), 5518].