M atom (M = Cu, Ag and Au) interaction with Ag and Au substrates: a first-principles study using cluster and slab models

J Phys Condens Matter. 2010 Nov 3;22(43):435001. doi: 10.1088/0953-8984/22/43/435001. Epub 2010 Oct 7.

Abstract

Using state-of-the-art first-principles calculations we report the interaction of M atoms (M = Cu, Ag and Au) with small Ag(n), Au(n) clusters (n = 3 and 6) and periodic Ag(111) and Au(111) surfaces. All calculations were performed using the plane wave pseudo-potential approach under the spin polarized version of the generalized gradient approximation scheme. The result shows that the equilibrium geometry of all MAg(3) and MAu(3) clusters favor a planar rhombus structure. From the charge distribution analysis of MAg(n)/MAu(n) clusters it is found that, while Cu and Ag donates electronic charge towards the host clusters, the Au atom acts as an acceptor, thus creating charge polarization in the system. The difference in orbital decomposed charges before and after the M interaction reveals that enhanced s-d hybridization is responsible for keeping the MAu(6) cluster planar, and increased p-orbital participation induces three-dimensional configurations in MAg(6) clusters. The optimization of M atom deposition on the Ag(111) and Au(111) surfaces shows that M atoms prefer to adsorb on the threefold fcc site over other well-defined sites. From the orbital decomposed charge analysis it is inferred that, although there is significant difference in the absolute magnitude of the interaction energy between M atoms and the Ag or Au substrates, the nature of chemical bonding is similar for the finite size clusters as well as in slab models.

MeSH terms

  • Adsorption
  • Copper / chemistry
  • Dimerization
  • Gold / chemistry
  • Metals, Heavy / chemistry*
  • Models, Molecular*
  • Molecular Conformation
  • Silver / chemistry
  • Surface Properties

Substances

  • Metals, Heavy
  • Silver
  • Gold
  • Copper