Dissociative Adsorption of O2 on Al(111): The Role of Orientational Degrees of Freedom.

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.