The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first-principles DFT study

A theoretical study of CH3 adsorbed on the (111) surface of some transition and noble metal surfaces M (M = Cu, Ni, Rh, Pt, Pd, Ag, Au) and on the Fe(100) is presented. We find that the hollow site is preferred more than the top one for Fe, Ni, Rh, and Cu, but it is the other way for Pt, Pd, Au, and Ag. In addition, a good linear relationship was observed between the chemisorption energy and d‐band center for Group VIII metals or the square of the coupling matrix element for Group IB metals at the hollow site. Interestingly, with a detailed comparison of the adsorption energies at the top and hollow sites, we find that the adsorption energies among each group are very similar on the top site, which supports the theoretical model of Hammer and Nørskov that the coupling between the HOMO of adsorbate and sp states of the metal is dominant and almost equal, and that the second coupling to the d‐band contributes less but reflects the change of the adsorption energy. It confirms that the coupling to the d band comprises two opposite factors, that is, the d‐band center was attractive and the square of the coupling matrix element was repulsive, such that the contributions from the two factors can counteract each other at the top site. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 871–878, 2005