Dissociation of O2 at Al(111):: The role of spin selection rules -: art. no. 036104

A most basic and puzzling enigma in surface science is the description of the dissociative adsorption of O-2 at the (111) surface of Al. Already for the sticking curve alone, the disagreement between experiment and results of state-of-the-art first-principles calculations can hardly be more dramatic. In this Letter we show that this is caused by hitherto unaccounted spin selection rules, which give rise to a highly nonadiabatic behavior in the O-2/Al(111) interaction. We also discuss problems caused by the insufficient accuracy of present-day exchange-correlation functionals.