title: Origin of the energy barrier to chemical reactions of O2 on Al(111): evidence for charge transfer, not spin selection.
abstract: Dissociative adsorption of molecular oxygen on the Al(111) surface exhibits mechanistic complexity that remains surprisingly poorly understood in terms of the underlying physics. Experiments clearly indicate substantial energy barriers and a mysteriously large number of adsorbed single oxygen atoms instead of pairs. Conventional first principles quantum mechanics (density functional theory) predicts no energy barrier at all; instead, spin selection rules have been invoked to explain the barrier. In this Letter, we show that correct barriers arise naturally when embedded correlated electron wave functions are used to capture the physics of the interaction of O(2) with the metal surface. The barrier originates from an abrupt charge transfer (from metal to oxygen), which is properly treated within correlated wave function theory but not within conventional density functional theory. Our potential energy surfaces also identify oxygen atom abstraction as the dominant reaction pathway at low incident energies, consistent with measurements, and show that charge transfer occurs in a stepwise fashion.
authors.affiliation: Department of Mechanical and Aerospace Engineering and Chemistry, Program in Applied and Computational Mathematics, and Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544, USA.
authors.forename: Florian
authors.initials: F
authors.lastname: Libisch
authors.forename: Chen
authors.initials: C
authors.lastname: Huang
authors.forename: Peilin
authors.initials: P
authors.lastname: Liao
authors.forename: Michele
authors.initials: M
authors.lastname: Pavone
authors.forename: Emily A
authors.initials: EA
authors.lastname: Carter