Nonadiabatic effects in the dissociation of oxygen molecules at the Al(111) surface

Abstract

The measured low initial sticking probability of oxygen molecules at the Al(111) surface that had puzzled the field for many years was recently explained in a nonadiabatic picture invoking spin-selection rules [J. Behler et al., Phys. Rev. Lett. 94, 036104 (2005)]. These selection rules tend to conserve the initial spin-triplet character of the free ${\mathrm{O}}_{2}$ molecule during the molecule's approach to the surface. A locally constrained density-functional theory approach gave access to the corresponding potential-energy surface (PES) seen by such an impinging spin-triplet molecule and indicated barriers to dissociation which reduce the sticking probability. Here, we further substantiate this nonadiabatic picture by providing a detailed account of the employed approach. Building on the previous work, we focus, in particular, on inaccuracies in present-day exchange-correlation functionals. Our analysis shows that small quantitative differences in the spin-triplet constrained PES obtained with different gradient-corrected functionals have a noticeable effect on the lowest kinetic energy part of the resulting sticking curve.