Quantifying the impact of vibrational nonequilibrium in plasma catalysis: insights from a molecular dynamics model of dissociative chemisorption

The rate, selectivity and efficiency of plasma-based conversion processes is strongly affected by nonequilibrium phenomena. High concentrations vibrationally excited molecules are such a plasma-induced effect. It frequently assumed that important in plasma catalysis because their presence lowers the apparent activation energy dissociative chemisorption reactions thus increases rate. A detailed atomic-level understanding stimulated catalytic context however lacking. Here, we couple recently developed statistical model vibrational to molecular dynamics simulations, enhanced sampling methods, machine learning techniques. We quantify impact on barrier H2 CH4 nickel catalysts over wide range temperatures. investigate effect surface structure compare role different modes methane dissociation process. For low temperatures, very high efficacies found, bend vibrations appears dominate methane. relative much higher terrace sites than steps. then show how our simulations can help interpret recent experimental results, suggest new paths better catalysis.