Effect of subsurface Ti-interstitials on the bonding of small gold clusters on rutile TiO(2)(110)

J Chem Phys. 2009 Jan 28;130(4):044704. doi: 10.1063/1.3055419.

Abstract

The density functional theory is used to examine the electronic structure of small Au clusters, supported on rutile TiO(2)(110) surfaces having subsurface Ti-interstitials. The interstitials reduce the surface and we find that negatively charged gold clusters are stabilized with respect to the stoichiometric surface. The behavior of the open-shell gold clusters can be rationalized in terms of the highest occupied molecular orbitals and the resulting electron affinities. The relative stabilities of closed-shell gold clusters led to recent disagreements in the literature. We show that they are very dependent on the density functional used. As expected, a redshift in the CO stretch vibration is calculated for CO adsorbed on a negatively charged cluster. Somewhat surprisingly a larger redshift is found for CO adsorbed on an overall positively charged Au(3) cluster. This is explained by CO being a local probe of the individual Au charges and one Au atom having an electron accumulation.

MeSH terms

  • Carbon Monoxide / chemistry
  • Cluster Analysis
  • Gold / chemistry*
  • Models, Chemical*
  • Polymers / chemistry
  • Static Electricity
  • Titanium / chemistry*

Substances

  • Polymers
  • titanium dioxide
  • Gold
  • Carbon Monoxide
  • Titanium