Concerning the Role of σ-Hole in Non-Covalent Interactions: Insights from the Study of the Complexes of ArBeO with Simple Ligands

The structure, stability, and bonding character of some exemplary LAr and L-ArBeO (L = He, Ne, Ar, N₂, CO, F₂, Cl₂, ClF, HF, HCl, NH₃) were investigated by MP2 and coupled-cluster calculations, and by symmetry-adapted perturbation theory. The nature of the stabilizing interactions was also assayed by the method recently proposed by the authors to classify the chemical bonds in noble-gas compounds. The comparative analysis of the LAr and L-ArBeO unraveled geometric and bonding effects peculiarly related to the σ-hole at the Ar atom of ArBeO, including the major stabilizing/destabilizing role of the electrostatic interactionensuing from the negative/positive molecular electrostatic potential of L at the contact zone with ArBeO. The role of the inductive and dispersive components was also assayed, making it possible to discern the factors governing the transition from the (mainly) dispersive domain of the LAr, to the σ-hole domain of the L-ArBeO. Our conclusions could be valid for various types of non-covalent interactions, especially those involving σ-holes of respectable strength such as those occurring in ArBeO.