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

Abstract

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.

Strengthening gold–gold bonds by complexing gold clusters with noble gases

“…Such transfer of negative charge from Kr to Au was also predicted in Ref. [10] on the basis of natural bond orbital analysis. This charge transfer is inconsistent with the strengthening of the Au\Au bond; in fact, the Au\Au bond in the Au 2 − is weaker (i.e., longer and with softer stretching frequency, see SI) than in Au 2 .…”

“…In most of the previous studies, electrostatic effects are expected to play a major role in the interaction between the RG atom(s) and Au, since the Au atom is either charged or is a part of a polar molecule (with a large dipole moment). Reports on theoretical analysis of the binding of RG atoms to bare neutral Au M clusters are very scarce [10].We find that the present understanding of RG-Au M interaction is not conclusive due to the sensitivity of RG-Au M electronic structure to the level of theory. Therefore, in this work we analyze bonding between RG atoms (Ne, Ar, Kr, and Xe) and the smallest Au M clusters (M = 2, 3) using a variety of different theoretical approaches.…”

“…In most of the previous studies, electrostatic effects are expected to play a major role in the interaction between the RG atom(s) and Au, since the Au atom is either charged or is a part of a polar molecule (with a large dipole moment). Reports on theoretical analysis of the binding of RG atoms to bare neutral Au M clusters are very scarce [10].…”

Electronic Structure Insights into the Solvation of Magnesium Ions with Cyclic and Acyclic Carbonates

“…For all interactions with significant sharing of electrons, H(r)i s negative, and its absolute value reflects ac ovalent interaction. [36] QTAIM analysis on the optimized structures wasp erformed at the M06-2X/6-311+ ++ +G(d,p) level (Table 2a nd ÀOb onds. This indicates that as trong bondinge nergy is associated with high S1(r)v alues at the BCPs.…”

Ab Initio Molecular Dynamics of Dimerization and Clustering in Alkali Metal Vapors

“…[1][2][3][4][5] All alkali metals are known to form diatomic molecules through the formation of weak metal-metal bonds. [6][7][8][9][10][11] The weak bond originates from the overlap between diffuse valence orbitals of two atoms, considered within the one-electron approximation.…”