Binding of Noble Metal Clusters with Rare Gas Atoms: Theoretical Investigation

Binding of noble metal clusters (M n , M = Cu, Ag, and Au; n = 2–4) with rare gas atoms (Rg = Kr, Xe, and Rn) has been investigated at the density functional (CAM-B3LYP) and ab initio (MP2) levels of theory. The calculation shows significant affinity of neutral metal clusters for interaction with rare gas atoms. The binding energies indicate that gold clusters have the highest and silver clusters have the lowest affinity for interaction with rare gas atoms, and for the same metal clusters, there is a continuous increase in E b from Kr to Rn. The M–Rg bonding mechanism have been interpreted by means of the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition analysis (EDA). According to these theories, the M–Rg bonds are found to be partially electrostatic and partially covalent. EDA results identify that these bonds have less than 40% covalent character and more than 60% electrostatic, and also NBO calculations predict the amount of charge transfer from the lone pair of rare gas to σ* and n*orbitals of metal clusters.