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Substituent effects on noncovalent halogen/π interactions: Theoretical study
Author(s) -
Lu YunXiang,
Zou JianWei,
Wang YanHua,
Yu QingSen
Publication year - 2006
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.21279
Subject(s) - chemistry , halogen , non covalent interactions , halogen bond , substituent , interaction energy , atoms in molecules , computational chemistry , benzene , ab initio , molecule , density functional theory , dispersion (optics) , electron density , charge density , chemical physics , electron , stereochemistry , organic chemistry , hydrogen bond , physics , quantum mechanics , alkyl
Abstract Noncovalent halogen/π interactions of FCl with substituted benzenes have been investigated using ab initio calculations. It was shown that the predicted maximum interaction energy gap between the substituted and unsubstituted systems amounts to 1.14 kcal/mol, and therefore substituents on benzene have a pronounced effect on the strength of halogen/π interactions. While the presence of electron‐donating groups (NH 2 , CH 3 , and OH) on benzene enhances the interaction energy appreciably, an opposite effect is observed for electron‐accepting groups (NO 2 , CN, Br, Cl, and F). The large gain of the attraction by electron correlation illustrates that the stabilities of the systems considered arise primarily from the dispersion interaction. Beside the dispersion interaction, the charge‐transfer interaction also plays an important role in halogen/π interactions, as a charge density analysis suggested. To provide more insight into the nature of halogen/π interactions, topological analysis of the electron density distribution and properties of bond critical points were determined in terms of the atoms in molecules (AIM) theory. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007