高等学校化学学报2012，Vol.33Issue(3)：541-547,7.DOI:10.3969/j.issn.0251-0790.2012.03.021
苯-卤素(X2,X=F,Cl,Br,I)相互作用本质的对称性匹配微扰理论研究
Symmetry-adapted Perturbation Theory Study on the Nature of Benzene-halogen(X2, X =F, Cl, Br, I)
摘要
Abstract
A theoretical study of the charge-transfer complexes ( CTC) , as defined by Mulliken, formed by benzene and dihalogen molecules X2(X = F, Cl, Br, I) was carried out with second-order M0ller-Plesset perturbation (MP2). In the global minimum of C6H6-X2(X= F, Cl, Br, I) , the halogen molecule is located above one of the C-C bond centers of benzene, and the halogen molecule bond axis also slightly tilts towards the axis perpendicular to the plane of the benzene ring. The natural bond orbital (NBO) analysis reveals that the number of charge-transfer is negligible for these charge-transfer complexes. Symmetry-adapted perturbation theory(SAPT) results show that the contribution of electrostatic effects to halogen bonding interactions is relatively small, and generally accounts for about 20% of the attractive interaction for the four complexes. Halogen bonding interaction in C6H6-F2 system is principally dispersive in nature. The halogen bonds containing chlorine, bromine and iodine are largely dependent on the induction type interactions. And, interestingly, more induction(and less dispersive) interaction appears from F to I. The so-called "charge-transfer complexes (CTC)" for C6H6-X2 system is not exact on electron correlation level.关键词
电荷转移复合物/苯/双卤分子/分子间相互作用/对称匹配微扰理论Key words
Charge-transfer complex ( CTC) /Benzene ( C6H6 ) /Dihalogens molecule ( X2) /Intermolecular interaction/Symmetry-adapted perturbation theory(SAPT)分类
化学化工引用本文复制引用
梁雪,孙涛,王一波..苯-卤素(X2,X=F,Cl,Br,I)相互作用本质的对称性匹配微扰理论研究[J].高等学校化学学报,2012,33(3):541-547,7.基金项目
国家自然科学基金(批准号:20463002)和贵州大学自然科学青年科研基金(批准号:2009068)资助. （批准号:20463002）
