Premium
Competition between halogen bond and hydrogen bond in complexes of superalkali Li 3 S and halogenated acetylene XCCH (X = F, Cl, Br, and I)
Author(s) -
Tian WenKai,
Li QingZhong
Publication year - 2015
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.24802
Subject(s) - halogen , chemistry , atom (system on chip) , halogen bond , acetylene , hydrogen atom , crystallography , electron localization function , hydrogen bond , computational chemistry , electron , molecule , group (periodic table) , alkyl , physics , organic chemistry , quantum mechanics , computer science , embedded system
Complexes of superalkali Li 3 S and XCCH (X = F, Cl, Br, and I) have been studied with theoretical calculations at the MP2/aug‐cc‐pVTZ level. Three types of structures are found: (A) the X atom combines with the S atom through a halogen bond; (B) the X atom interacts with the π electron of Li 3 S by a π halogen bond; (C) the H atom combines with the S atom through a hydrogen bond. For A and B, a heavier halogen atom makes the interaction stronger, while for C, the change of interaction energy is not obvious, showing a small dependence on the nature of the X atom in HCCX. A is more stable than B and their difference in stability decreases as X varies from Cl to I. For the F and Cl complexes, A is weaker than C, however, the former is stronger than the latter in the Br and I complexes. The above three types of interactions have been analyzed by means of electron localization function, electron density difference, and energy decomposition, and the results show that they have similar nature and features with conventional interactions. © 2014 Wiley Periodicals, Inc.