Density Functional Study of the Interaction of Carbon Monoxide with Small Neutral and Charged Silver Clusters

Abstract

CO adsorption on small neutral, anionic, and cationic silver clusters Ag(n) (n = 1-7) has been studied with use of the PW91PW91 density functional theory (DFT) method. The adsorption of CO on-top site, among various possible sites, is energetically preferred irrespective of the charge state of the silver cluster. The cationic silver clusters generally have a greater tendency to adsorb CO than the anionic and neutral silver ones, except for n = 3 and 4, and the binding energies reach a local minimum at n = 5. The binding energies on the neutral clusters, instead, reach a local maximum at n = 3, which is about 0.87 eV, probably large enough to be captured in the experiments. Binding of CO to the silver clusters is generally weaker than that to the copper and gold counterparts at the same size and charge state. This is due to the weaker orbital interaction between silver and CO, which is caused by the larger atomic radius of the silver atom. In contrast, Au atoms with a larger nuclear charge but a similar atomic radius to silver owing to the lanthanide contraction are able to have a stronger interaction with CO.