First-principles kinetic Monte Carlo simulations for heterogeneous catalysis: Application to the CO oxidation at RuO2(110)

We describe a first-principles statistical mechanics approach enabling us to simulate the steady-state situation of heterogeneous catalysis. In a first step, density-functional theory together with transition-state theory is employed to obtain the energetics of the relevant elementary processes. Subsequently the statistical mechanics problem is solved by the kinetic Monte Carlo method, which accounts for the correlations, fluctuations, and spatial distributions of the chemicals at the surface of the catalyst under steady-state conditions. Applying this approach to the catalytic oxidation of CO at RuO2(110), we determine the surface atomic structure and composition in reactive environments ranging from ultra-high vacuum (UHV) to technologically relevant conditions, i.e., up to pressures of several atmospheres and elevated temperatures. We also compute the CO2 formation rates (turnover frequencies). The results are in quantitative agreement with all existing experimental data. We find that the high catalytic activity of this system is intimately connected with a disordered, dynamic surface phase with significant compositional fluctuations. In this active state the catalytic function results from a self-regulating interplay of several elementary processes.