Determination of the basic timescale in kinetic Monte Carlo simulations by comparison with cyclic-voltammetry experiments

Abstract

While kinetic Monte Carlo simulations can provide long-time simulations of the dynamics of physical and chemical systems, it is not yet possible in general to identify the inverse Monte Carlo attempt frequency with a physical timescale. Here we demonstrate such an identification by comparing simulations with experimental data. Using a dynamic lattice-gas model for the electrosorption of Br on Ag(100), we measure the scan-rate dependence of the separation between positive-and negative-going peaks in cyclic-voltammetry (CV) and compare simulated and experimental peak separations. By adjusting the Monte Carlo attempt frequency, good agreement between simulated and experimental peak separations is achieved. It is also found that the uniqueness of such a determination is dependent on the relative values of the adsorption/desorption and diffusion free-energy barriers.

Accepted for publication in Surface Science Letters,8 pages, 4 figures

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Cited by in corpus (6)

• Cl electrosorption on Ag(100): Lateral interactions and electrosorption valency from comparison of Monte Carlo simulations with chronocoulometry experiments
• Kinetic Monte Carlo simulations of electrodeposition: Crossover from continuous to instantaneous homogeneous nucleation within Avrami's law
• Microstructure and velocity of field-driven solid-on-solid interfaces moving under stochastic dynamics with local energy barriers
• New Cyclic Voltammetry Method for Examining Phase Transitions: Simulated Results
• Applications of Computer Simulations and Statistical Mechanics in Surface Electrochemistry
• Dynamics of Desorption with Lateral Diffusion