Unusual halogen-bonded complex FBrδ+⋯Brδ+F and hydrogen-bonded complex FBrδ+⋯Hδ+F formed by interactions between two positively charged atoms of different polar molecules

• Published in: The Journal of chemical physics 2007-04, Vol.126 (14)
• Main Authors: Wang, Fang-Fang, Hou, Jian-Hua, Li, Zhi-Ru, Wu, Di, Li, Ying, Lu, Zhong-Yuan, Cao, Wei-Liang
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.2715559

Using ab initio calculations, the authors’ predicted for the first time that the halogen-bonded complex FBrδ+⋯Brδ+F and hydrogen-bonded complex FBrδ+⋯Hδ+F formed by the interactions between two positively charged atoms of different polar molecules can be stable in gas phase. It shows that halogen bond or hydrogen bond not only exists between oppositely charged atoms but also between like-charged atoms. That the attraction arising from the special halogen bond or hydrogen bond can exceed the electrostatic repulsion between two contact positively charged atoms stabilizes the complex. Of course, from the point of view of physics they can consider the interactions in FBrδ+⋯Brδ+F and FBrδ+⋯Hδ+F as mainly the sum of the long range molecular interactions, namely, electrostatic, induction, and dispersion with some short-range repulsion. They found that the intermolecular electron correlation contribution representing dispersion interaction plays a crucial role in the stabilities of seemingly repulsive complexes FBrδ+⋯Brδ+F and FBrδ+⋯Hδ+F.