First-principles calculations of the phonon dispersion curves of H on Pt(111)

Abstract

We have calculated the surface phonon dispersion curves for H on Pt(111), using first-principles, total energy calculations based on a mixed-basis set and norm-conserving pseudopotentials. Linear response theory and the harmonic approximation are invoked. For one monolayer of H in the preferred adsorption site (fcc hollow) vibrational modes polarized parallel and perpendicular to the surface are found, respectively, at 73.5 meV and 142.6 meV, at the Γ point of the surface Brillouin zone. The degeneracy of the parallel mode is lifted at the zone boundaries, yielding energies of 69.6 meV and 86.3 meV at the M point and 79.4 meV and 80.8 meV at the K point. The dispersion curves for H adsorption at the hcp hollow site differ only slightly from the above. In either case, H adsorption has considerable impact on the substrate modes; in particular the surface mode in the gap in the bulk phonon spectrum (around M point) is pushed into the bulk band. For on-top H adsorption, modes polarized parallel and perpendicular to the surface have respective energies of 47.4 meV and 277.2 meV, at the Γ point. The former disperses to 49.1 meV and 59.5 meV at the M point and to 56 meV and 56.7 meV at the K point. The H vibrational mode polarized perpendicular to the surface shows little dispersion, in all three cases considered. Insights are obtained from the hybridization of the H and Pt electronic states.