Reaction-Induced Excitations and Their Effect on Surface Chemistry

Despite intensive study of reactions on metals, it is unclear whether electronic excitations play an important role. Here, we show that nonadiabatic effects do indeed play a significant role in N 2 and H 2 dissociation on Ru nanoparticles. We employ nonadiabatic dynamical calculations based on real-time, time-dependent density functional theory to study energy dissipation during these exothermic reaction steps. We find that dissipation of the excess energy into excitation of electrons exceeds thermal dissipation into phonons. For isolated dissociation events, electronic friction can increase reaction barriers; furthermore, the excitations induced by a dissociation event can affect other reacting molecules. Our studies suggest that, for exothermic reactions, metal catalysts in reaction conditions may be constantly experiencing electronic excitations, and these excitations can significantly affect surface chemistry.