title: On the physical nature of halogen bonds: a QTAIM study.
abstract: In this article, we report a detailed study on halogen bonds in complexes of CHCBr, CHCCl, CH2CHBr, FBr, FCl, and ClBr with a set of Lewis bases (NH3, OH2, SH2, OCH2, OH(-), Br(-)). To obtain insight into the physical nature of these bonds, we extensively used Bader's Quantum Theory of Atoms-in-Molecules (QTAIM). With this aim, in addition to the examination of the bond critical points properties, we apply Pendás' Interacting Quantum Atoms (IQA) scheme, which enables rigorous and physical study of each interaction at work in the formation of the halogen-bonded complexes. In particular, the influence of primary and secondary interactions on the stability of the complexes is analyzed, and the roles of electrostatics and exchange are notably discussed and compared. Finally, relationships between QTAIM descriptors and binding energies are inspected.
authors.affiliation: Normandy Université, COBRA UMR 6014 and FR 3038 , Université de Rouen , INSA Rouen, CNRS, 1 rue Tesniére, 76821 Mont Saint Aignan, Cedex, France.
authors.forename: Olga A
authors.initials: OA
authors.lastname: Syzgantseva
authors.forename: Vincent
authors.initials: V
authors.lastname: Tognetti
authors.forename: Laurent
authors.initials: L
authors.lastname: Joubert
mesh_terms: D004579:Electron Transport; D006219:Halogens / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D055585:Physical Phenomena; D011789:Quantum Theory; D055672:Static Electricity
chemical_list: D006219:Halogens