Bond Analysis in Dihalogenâ\u80\u93Halide and Dihalogenâ\u80\u93Dimethylchalcogenide Systems

The bonding in mixed chalcogen/halogen three-body systems of general formula XI···Y (X = Cl, Br, I; Y = Iâ\u80\u93, EMe2; E = S, Se, Te) is theoretically examined by using different methodologies, namely: charge-displacement (CD) analysis, which quantifies the electronic flux throughout the whole adduct; the energy decomposition analysis combined with natural orbital for chemical valence (EDA-NOCV) method; and zeroth order symmetry adapted perturbation theory (SAPT0), where the latter two methods decompose the contributions of the interaction energy between XI and Y into physically meaningful terms. In the solid state, the distribution of the relative elongations of the two bonds (δXIand δIY) in the three-body systems examined here can be rationalized in terms of only one common equation derived from the bond-valence model. According to CD and EDA-NOCV, the charge transfer between the two fragments does not depend on the exact nature of the atoms involved, but only on the values of δXIand δIY, with a variability of 0.05 e, and on the total charge of the system. On the other hand, using the SAPT0 method and computing the polarization-free value of the charge transfer between the two fragments, the results are the same for all of the systems with the same δXIand δIY, irrespectively not only of the nature of the atoms, but also of the total charge of the system (anionic and neutral)