An off-lattice model for Br electrodeposition on Au(100): from DFT to experiment

Abstract

Since Br adsorption on Au(100) displays an incommensurate ordered phase, a lattice-gas treatment of the adlayer configurations is not reliable. We therefore use density functional theory slab calculations to determine the parameters necessary for the construction of an off-lattice model. We compute and analyze the total energy and electron density as the lateral Br position and coverage are varied. This allows the calculation of the corrugation potential, the short-range lateral interactions, the dipole moment (long-range interactions), and the residence charge. From these parameters, we construct an off-lattice model with no freely adjustable parameters.The simulation results compare remarkably well with experimental results.

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“…This CDD can be further visualized by using additional software tools, such as VESTA . Charge distributions in the bare surface and in the adsorbed molecule are obtained by assuming that these partial systems have the same geometry as that in the composite system (comprised of the surface and the adsorbate), as described elsewhere. , …”

Competitive adsorption of hydrogen and bromide on Pt(100): Mean-field approximation vs. Monte Carlo simulations

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Parameter estimation by Density Functional Theory for a lattice-gas model of Br and Cl chemisorption on Ag (100)

“…We define the negative of the electron densities from the DFT output as the charge density distributions ρ( x), and we introduce the charge transfer function per adsorbed atom, which is defined as follows [22] ∆ρ where ρ( x) halide−Ag(100) is the full charge density of the adlayer system with N adsorbed Br or Cl on each side of the slab, and ρ( x) halide is the full charge density of the pair of isolated halide atoms at the same positions as in the halide-Ag bonded system, and ρ( x) Ag(100) is the charge density of the Ag(100) slab with all atoms at the same positions as in the halide-Ag bonded system [23]. After integrating over x and y, this yields the charge transfer function per pair of adsorbed atoms,…”