Size and charge effects on the binding of CO to late transition metal clusters

We report on the size and charge dependence of the C–O stretching frequency, ν(CO), in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters (ConCO–/0/+), anionic, neutral, and cationic rhodium clusters (RhnCO–/0/+), and cationic nickel clusters (NinCO+) for n up to 37. We develop models, based on the established vibrational spectroscopy of organometallic carbonyl compounds, to understand how cluster size and charge relate to ν(CO) in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO π* orbital. Electrostatic effects play a significant but minor role. For the charged clusters, the size trends are related to the dilution of the charge density at the binding site on the cluster as n increases. At large n, ν(CO) approaches asymptotes that are not the same as found for ν(CO) on the single crystal metal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites