Argon Adsorption on Cationic Gold Clusters Au(n)(+) (n ≤ 20)

The interaction of Au(n)(+) (n ≤ 20) clusters with Ar is investigated by combining mass spectrometric experiments and density functional theory calculations. We show that the inert Ar atom forms relatively strong bonds with Au(n)(+). The strength of the bond strongly varies with the cluster size and is governed by a fine interplay between geometry and electronic structure. The chemical bond between Au(n)(+) and Ar involves electron transfer from Ar to Au, and a stronger interaction is found when the Au adsorption site has a higher positive partial charge, which depends on the cluster geometry. Au(15)(+) is a peculiar cluster size, which stands out for its much stronger interaction with Ar than its neighbors, signaled by a higher abundance in mass spectra and a larger Ar adsorption energy. This is shown to be a consequence of a low-coordinated Au adsorption site in Au(15)(+), which possesses a large positive partial charge.