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Bond Analysis in Dihalogen–Halide and Dihalogen–Dimethylchalcogenide Systems
Author(s) -
Schneider Felipe S. S.,
Caramori Giovanni Finoto,
Parreira Renato L. T.,
Lippolis Vito,
Arca Massimiliano,
Ciancaleoni Gianluca
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701337
Subject(s) - chemistry , valence (chemistry) , chalcogen , computational chemistry , halogen , valence bond theory , halide , crystallography , atomic physics , quantum mechanics , molecule , molecular orbital , inorganic chemistry , physics , organic chemistry , alkyl
The bonding in mixed chalcogen/halogen three‐body systems of general formula XI ··· Y (X = Cl, Br, I; Y = I – , EMe 2 ; 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 ( δ XI and δ IY ) 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 δ XI and δ IY , 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 δ XI and δ IY , irrespectively not only of the nature of the atoms, but also of the total charge of the system (anionic and neutral).