The Steady State of Heterogeneous Catalysis, Studied by First-Principles Statistical Mechanics

The turnover frequency of the catalytic oxidation of CO at RuO₂(110) was calculated as a function of temperature and partial pressures using ab initio statistical mechanics. The underlying energetics of the gas-phase molecules, dissociation, adsorption, surface diffusion, surface chemical reactions, and desorption were obtained by all-electron density-functional theory. The resulting CO₂ formation rate [in the full (T,p_CO,p_O2) space], the movies displaying the atomic motion and reactions over times scales from picoseconds to seconds, and the statistical analyses provide insight into the concerted actions ruling heterogeneous catalysis and open thermodynamic systems in general.