Hot atom chemistry: Oxygen at stepped platinum surfaces

It is a paradigm in chemistry that chemical reactions are mainly governed by thermodynamics. Within this assumption, reaction rates can be derived from transition state theory which requires a quasi-equilibrium between reactants and activated transition state complexes that is achieved through friction. However, to reach thermal equilibrium through friction takes some time. Here we show, based on ab initio molecular dynamics simulations of the interaction of molecular oxygen with stepped Pt surfaces, that chemical reactions in heterogeneous catalysis can occur in a non-equilibrium fashion when the excess kinetic energy upon entering the potential well of a reaction intermediate is large enough.