Heterogeneous catalysis is of paramount importance in chemistry and energy applications. Catalysts that couple light energy into chemical reactions in a directed, orbital-specific manner would greatly reduce the energy input requirements of chemical transformations, revolutionizing catalysis-driven chemistry. Here we report the room temperature dissociation of H(2) on gold nanoparticles using visible light. Surface plasmons excited in the Au nanoparticle decay into hot electrons with energies between the vacuum level and the work function of the metal. In this transient state, hot electrons can transfer into a Feshbach resonance of an H(2) molecule adsorbed on the Au nanoparticle surface, triggering dissociation. We probe this process by detecting the formation of HD molecules from the dissociations of H(2) and D(2) and investigate the effect of Au nanoparticle size and wavelength of incident light on the rate of HD formation. This work opens a new pathway for controlling chemical reactions on metallic catalysts.
The interaction between O2 molecules and Al surfaces has long been poorly understood despite its importance in diverse chemical phenomena. Early experimental investigations of adsorption dynamics indicated that abstraction of a single O atom by the surface, instead of dissociative chemisorption, dominates at low O2 incident kinetic energies. Abstraction of the closer O atom suggests low barrier heights at perpendicular incidence. However, recent measurements suggest that parallel O2 orientations dominate sticking at low energies. We resolve this apparent contradiction by a systematic ab initio embedded correlated wavefunction study of the stereochemistry of O2 reacting with Al(111). We identify two important new details: (i) initially, roughly parallel oxygen molecules tend to tilt upright while approaching the surface, suggesting that the abstraction channel does dominate at low energies and (ii) the reaction channel with the lowest barrier indeed corresponds to a parallel orientation, which ultimately evolves either into dissociative chemisorption or toward abstraction.
Plasmons / Photocatalysis / Potential Energy SurfacesNoble metal surfaces play a central role in heterogeneous catalysis. Lasers of the appropriate resonance frequency efficiently generate surface plasmons. These, in turn, may generate hot electrons, which can drive catalytic reactions at low temperatures. In this work, we demonstrate how embedding methods allow for the use of accurate ab-initio correlated wavefunction methods to describe excited-state potential energy surfaces of molecule-surface interactions. As model system, we consider the hot-electron-induced dissociation of hydrogen on Au(111), which has recently been demonstrated experimentally. We discuss merits and limitations of several different correlated wavefunction schemes. Our results show that dissociation barriers may be substantially reduced upon electron excitation and suggest a method to calculate the hot electron energies required for catalytic reactions.
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