CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set

Abstract

We present a detailed study of the adsorption of CO on Cu, Rh, and Pt (111) surfaces in top and hollow sites. The study has been performed using the local density approximation, the gradient corrected functional PBE, and the hybrid Hartree-Fock density functionals PBE0 and HSE03 within the framework of generalized Kohn-Sham density functional theory using a plane-wave basis set. As expected, the local density approximation and generalized gradient approximation functionals show a tendency to favor the hollow sites, at variance with experimental findings that give the top site as the most stable adsorption site. The PBE0 and HSE03 functionals reduce this tendency. In fact, they predict the correct adsorption site for Cu and Rh but fail for Pt. However, even in this case, the hybrid functional destabilizes the hollow site by $50\mathrm{meV}$ compared to the PBE functional. The results of the total energy calculations are presented along with an analysis of the projected density of states.