The nature of inter- and intramolecular interactions in F2OXe…HX (X= F, Cl, Br, I) complexes

Abstract

Electronic structure of the XeOF2 molecule and its two complexes with HX (X= F, Cl, Br, I) molecules have been studied in the gas phase using quantum chemical topology methods: topological analysis of electron localization function (ELF), electron density, ρ(r), reduced gradient of electron density |RDG(r)| in real space, and symmetry adapted perturbation theory (SAPT) in the Hilbert space. The wave function has been approximated by the MP2 and DFT methods, using APF-D, B3LYP, M062X, and B2PLYP functionals, with the dispersion correction as proposed by Grimme (GD3). For the Xe-F and Xe=O bonds in the isolated XeOF2 molecule, the bonding ELF-localization basins have not been observed. According to the ELF results, these interactions are not of covalent nature with shared electron density. There are two stable F2OXe…HF complexes. The first one is stabilized by the F-H…F and Xe…F interactions (type I) and the second by the F-H…O hydrogen bond (type II). The SAPT analysis confirms the electrostatic term, Eelst (1) and the induction energy, Eind (2) to be the major contributors to stabilizing both types of complexes.