HNgBeF₃(Ng = Ar‐Rn): Superhalogen‐supported noble gas insertion compounds

Abstract

Abstract Ab initio and density functional theory‐based calculations are performed to study the structure, stability, and nature of bonding of superhalogen‐supported noble gas (Ng) compounds of the type HNgY where (Ng = Ar‐Rn; Y = BeF 3 ). Here, BeF 3 acts as the superhalogen. Calculations show that the HNgBeF 3 spontaneously dissociates into product following the dissociation channels: HNgBeF 3 → HBeF 3 + Ng and HNgBeF 3 → Ng + HF + BeF 2 . The transition states are optimized and the energy barriers are computed to show the metastable behavior of HNgBeF 3 . HNgBeF 3 molecules are kinetically stable with respect to the first dissociation process having energy barriers of 1.0, 5.0, 10.6, and 13.9 kcal/mol for Ar, Kr, Xe, and Rn analogues, respectively, at CCSD(T)/Aug‐cc‐pVTZ level. These calculations suggest that the HXeBeF 3 and HRnBeF 3 can be shown to be stable up to ∼100 K temperature with a half‐life of ∼10 2 seconds. The nature of HNg and two different types of NgF bonds in HNgBeF 3 molecules is explored through the natural bond orbital and electron density analyses. The large Wiberg bond index (WBI) values for the HNg bond indicate the formation of almost a single bond in between H‐atoms and Ng‐atoms, whereas small WBI values for the two NgF bonds indicate a noncovalent interaction in between them. The electron density analysis further supports the covalency of the HNg bond and noncovalent interaction in the two NgF bonds in HNgBeF 3 .