We performed the first comprehensive analysis of the intermolecular interaction energy and anharmonic vibrations of 41 structures of the HXeY···HX (X, Y = F, Cl, Br, I) family of noble-gas-compound complexes for all possible combinations of Y and X. New structures are found and the interaction energy is studied by means of the symmetry-adapted perturbation theory up to the second-order corrections providing insight into the physical nature of the interaction in the complexes. The energy components are discussed in connection to anharmonic frequency analysis. The results show that the induction and dispersion corrections are the main driving forces of the interaction and their relative contributions correlate with the complexation effects seen in the vibrational stretching modes of Xe-H and H-X. Rather clear patterns of interaction are found for different structures. Our findings corroborate previous findings with better methods and provide new data. The results suggest that the entire group of the studied complexes can be labelled as ''naturally blue-shifting'' except for the complexes with HI.

A comprehensive analysis of the intermolecular interaction energy and anharmonic vibrations of 41 structures of the HXeY⋯HX (X, Y = F, Cl, Br, I) family of noble-gas-compound complexes for all possible combinations of Y and X was conducted. New structures were identified, and their interaction energies were studied by means of symmetry-adapted perturbation theory, up to second-order corrections: this provided insight into the physical nature of the interaction in the complexes. The energy components were discussed, in connection to anharmonic frequency analysis. The results show that the induction and dispersion corrections were the main driving forces of the interaction, and that their relative contributions correlated with the complexation effects seen in the vibrational stretching modes of Xe–H and H–X. Reasonably clear patterns of interaction were found for different structures. Our findings corroborate previous findings with better methods, and provide new data. These results suggest that the entire group of the studied complexes can be labelled as “naturally blueshifting”, except for the complexes with HI.