Low O2 dissociation barrier on Pt(111) due to adsorbate-adsorbate interactions.

Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Rd, Menlo Park, California 94025, USA.
The Journal of Chemical Physics (Impact Factor: 3.16). 12/2010; 133(22):224701. DOI: 10.1063/1.3512618
Source: PubMed

ABSTRACT O(2) dissociation on Pt(111) has been followed at low and saturation coverage using temperature-programmed x-ray photoelectron spectroscopy and simulated with mean-field kinetic modeling, yielding dissociation (E(a)) and desorption (E(d)) barriers of 0.32 and 0.36 eV, respectively. Density functional theory calculations show that E(a) is strongly influenced by the O-O interatomic potential in the atomic final state: of the supercells considered, that which maximizes attractive third-nearest-neighbor interactions in the atomic final state yields both the lowest computed dissociation barrier (0.24 eV) and the best agreement with experiment. It is proposed that the effect of adsorbate-adsorbate interactions must be considered when modeling catalytic processes involving dissociative steps.

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