Alignment and impact angular dependence to O2 sticking and dissociation on Pt(111) and close-packed steps

Abstract

Oxygen's interaction with Pt surfaces serves as a model system in the development of an accurate theoretical description of reaction mechanisms that involve multiple precursor states. To benchmark the influence of surface structure on the dynamics of this interaction, we report absolute values of the initial sticking probability of O₂ onto Pt(111) and two vicinal surfaces for state-selected and rotationally-aligned O₂ molecules. Sticking probabilities vary significantly for helicoptering and cartwheeling molecules. Our data can be understood if normal energy scaling holds for all molecular orientations relative to the surface. Vicinal surfaces are much more reactive than Pt(111) with little to no dependence on the molecule's alignment and a more complex angular dependence. At low incident energies, sticking probabilities are highest for incidence into step facets. The weak alignment dependence points toward predominant scattering into a physisorbed state preceding chemisorbed states over a wide angular range.