Factors that influence hydrogen binding at metal-atop sites

The d-band model has proven to be effective for understanding trends in the chemisorption of various adsorbates on transition metal surfaces. However, hydrogen adsorption at the atop site of transition metals and their bimetallic alloy surfaces do not always correlate well with the d-band center of the adsorption site. Additionally, the d-band model cannot explain the disappearance of the local minima for H adsorption at the hollow site on the potential energy surface of 5d single-atom element doped Au and Ag(111) surfaces. Here, we use a simple model with factors, including the d-band center, filling of the d-band, renormalized adsorbate states, coupling matrix elements, and surface–adsorbate bond lengths, to correlate with the density functional theory calculated H binding energies on both mono- and bimetallic (111) surfaces. Our results suggest that H adsorption at metal-atop sites is determined by all these factors, not only by the d-band center. The strong adsorption of H at the atop sites of 5d metal surfaces can be explained by their lower repulsive contribution.