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

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. (C) 2010 American Institute of Physics. [doi:10.1063/1.3512618]