Deleterious effects of long-range self-repulsion on the density functional description of O2 sticking on aluminum.
Density functional theory (DFT) with semilocal functionals such as the local-density and generalized gradients approximations predicts that the dissociative adsorption of oxygen on Al (111) goes through without a barrier in stark contradiction to experimental findings. This problem motivated our study of the reaction of oxygen colliding with a small aluminum cluster Al(5). We found semilocal functionals predict a minute barrier to sticking, associated with smeared long-range charge transfer from the metal to the oxygen. Hybrid B3LYP predicts a larger barrier while the range-separated the Baer-Neuhauser-Livshits (BNL, Phys. Chem. Chem. Phys. 2007, 9, 2932.) functional finds a more prominent barrier. BNL predicts short-ranged and more abrupt charge transfer from the surface to the oxygen. We conclude that spurious self-repulsion inherent in semilocal functionals causes early electron-transfer, long-range attraction toward the surface and low reaction barriers for these systems. The results indicate that the missing DFT barrier for O(2) sticking on Al (111) may be due to spurious self-repulsion.
Institute of Chemistry and the Fritz Haber Center for Molecular Dynamics, the Hebrew University of Jerusalem, Jerusalem 91904 Israel.
Ester
E
Livshits
Roi
R
Baer
Ronnie
R
Kosloff