Dissociation of O2 at A1(111): The role of spin selection rules

Abstract

A most basic and puzzling enigma in surface science is the description of the dissociative adsorption of O2 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/A1(111) interaction. We also discuss problems caused by the insufficient accuracy of present-day exchange-correlation functionals. © 2005 The American Physical Society.