Static and Dynamic Monte Carlo Simulations of Br Electrodeposition on Ag(100)

Physics – Condensed Matter – Materials Science

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28 pages, 15 figures. Higher quality figures and movies are available at http://www.csit.fsu.edu/~rikvold Version updated with

Scientific paper

10.1016/S0039-6028(00)00892-X

We study the static and dynamic properties of bromine electrosorption onto single-crystal silver (100) electrodes by Monte Carlo simulation. At room temperature the system displays a second-order phase transition between a low-coverage disordered phase at more negative electrode potentials and a c(2x2) ordered phase with bromine coverage 1/2 at more positive potentials. We explore the phase diagram and demonstrate that the broad shoulder observed in room-temperature cyclic voltammograms is due to local fluctuations resembling ordered phases with coverage 1/4 which exist in the model at much lower temperatures. We construct a dynamic Monte Carlo algorithm using a thermally activated stochastic barrier-hopping model for the microscopic dynamics. We use this algorithm to study the phase ordering and disordering processes following sudden potential steps between the disordered phase and the c(2x2) phase and to study the sweep-rate dependence in simulated cyclic-voltammetry experiments.

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