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Hydrogen bond and σ‐hole interaction in M 2 C=S···HCN (M = H, F, Cl, Br, HO, H 3 C, H 2 N) complex: Dual roles of C=S group and substitution effect
Author(s) -
Jing Bo,
Li Qingzhong,
Gong Baoan,
Li Ran,
Liu Zhenbo,
Li Wenzuo,
Cheng Jianbo,
Sun Jiazhong
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23006
Subject(s) - chemistry , halogen , hydrogen bond , ab initio , crystallography , acceptor , interaction energy , halogen bond , hydrogen , ab initio quantum chemistry methods , stereochemistry , computational chemistry , molecule , alkyl , physics , organic chemistry , condensed matter physics
Abstract An ab initio computational study of the dual functions of CS group in the M 2 CS ··· HCN (M = H, F, Cl, Br, HO, H 3 C, H 2 N) complex has been performed at the MP2(Full)/aug‐cc‐pVTZ level. The CS group can act as both the electron donor and acceptor, thus two minima complexes were found for each molecular pairs. The interaction energy of hydrogen bond in the F, Cl, or Br substituted complexes is less negative than that in the corresponding H 2 CS one, while the interaction energy of the σ‐hole interaction is more negative. The OH substitution weakens the hydrogen bond, whereas the H 3 C and H 2 N substitution strengthens it. The σ‐hole interaction in the HO, H 3 C, and H 2 N complexes is very weak. The substitution effect has been understood with electrostatic induction and conjugation effects. The energy decomposition analysis has been performed for the halogen‐substituted complexes. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012.