TY - JOUR
T1 - Origin of the energy barrier to chemical reactions of O 2 on Al(111)
T2 - Evidence for charge transfer, not spin selection
AU - Libisch, Florian
AU - Huang, Chen
AU - Liao, Peilin
AU - Pavone, Michele
AU - Carter, Emily A.
PY - 2012/11/8
Y1 - 2012/11/8
N2 - 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.
AB - 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.
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U2 - 10.1103/PhysRevLett.109.198303
DO - 10.1103/PhysRevLett.109.198303
M3 - Article
C2 - 23215432
AN - SCOPUS:84869020076
SN - 0031-9007
VL - 109
JO - Physical review letters
JF - Physical review letters
IS - 19
M1 - 198303
ER -