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Deleterious Effects of Long-Range Self-Repulsion on the Density Functional Description of O2 Sticking on Aluminum†
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Section:Abstract
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 Al5. 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 O2 sticking on Al (111) may be due to spurious self-repulsion.
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History
- Published In Issue July 02, 2009
- Article ASAPMay 05, 2009
- Received: January 30, 2009
Revised: April 2, 2009
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