Communications: Exceptions to the d -band model of chemisorption on metal surfaces: The dominant role of repulsion between adsorbate states and metal d -states

摘要

We show that there is a family of adsorbate-substrate systems that do not follow the trends in adsorption energies predicted by the d -band model. A physically transparent model is used to analyze this phenomenon. We found that these adsorbate-substrate pairs are characterized by the repulsive interaction of the substrate d -band with the renormalized adsorbate states. The exceptions to the d -band model are mainly associated with the adsorbates having almost completely filled valence shell, and the substrates with nearly fully occupied d -band, e.g., OH, F, or Cl adsorption on metals and alloys characterized by d~9 or d~(10) substrate surface atoms.