CO on Pt(111) puzzle: A possible solution

CO adsorption on the Pt(111) surface is studied using first-principles methods. As found in a recent study [Feibelman et al., J. Phys. Chem. B 105, 4018 (2001)], we find the preferred adsorption site within density functional theory to be the hollow site, whereas experimentally it is found that the top site is preferred. The influence of pseudopotential and exchange-correlation functional error on the CO binding energy and site preference is carefully investigated. We also compare the site preference energy of CO on Pt(111) with the reaction energy of formaldehyde formation from ${\mathrm{H}}_2$ and CO. We show that the discrepancies between the experimental and theoretical results are due to the generalized gradient approximation (GGA) treating different bond orders with varying accuracy. We can therefore expect that GGA results will contain significant error whenever bonds of different bond order are broken and formed.