Stability of Noble-Gas-Bound SiH3+Clusters

Abstract

The stability of noble gas (Ng)-bound SiH3+ clusters is explored by ab initio computations. Owing to a high positive charge (+1.53 e−), the Si center of SiH3+ can bind two Ng atoms. However, the SiNg dissociation energy for the first Ng atom is considerably larger than that for the second one. As we go down group 18, the dissociation energy gradually increases, and the largest value is observed for the case of Rn. For NgSiH3+ clusters, the Ar–Rn dissociation processes are endergonic at room temperature. For He and Ne, a much lower temperature is required for it to be viable. The formation of Ng2SiH3+ clusters is also feasible, particularly for the heavier members and at low temperature. To shed light on the nature of SiNg bonding, natural population analysis, Wiberg bond indices computations, electron-density analysis, and energy-decomposition analysis were performed. Electron transfer from the Ng centers to the electropositive Si center occurs only to a small extent for the lighter Ng atoms and to a somewhat greater extent for the heavier analogues. The SiXe/Rn bonds can be termed covalent bonds, whereas the SiHe/Ne bonds are noncovalent. The SiAr/Kr bonds possess some degree of covalent character, as they are borderline cases. Contributions from polarization and charge transfer and exchange are key terms in forming SiNg bonds. We also studied the effect of substituting the H atoms of SiH3+ by halide groups (X) on the Ng binding ability. SiF3+ showed enhanced Ng binding ability, whereas SiCl3+ and SiBr3+ showed a lower ability to bind Ng than SiH3+. A compromise originates from the dual play of the inductive effect of the X groups and X→Si π backbonding (pz–pz interaction).