摘要
运用量子化学密度泛函B3LYP方法,采用6-311++G(d,p)及aug-cc-pVDZ基组,通过CP校正的几何梯度优化对(CH2)2O和(CH2)2S与双卤分子XY(XY=Cl2,Br2,ClF,BrF,BrCl)形成的卤键复合物的几何构型、振动频率和相互作用能等进行了研究.利用电子密度拓扑分析理论方法对卤键复合物的拓扑性质进行了分析研究,探讨了该类分子间卤键的作用本质.结果表明,(CH2)2O和(CH2)2S与双卤分子间的卤键介于共价键与离子键之间,偏于静电作用成分为主.形成卤键后,双卤分子的键长增加,振动频率减小,原子积分性质发生改变.卤键键长的变化、键能的强弱、键鞍点处的电子密度值与双卤分子的电负性有关.
Geometries, vibrational frequencies and thiirane…XY （XY=Cl2, Br2, ClF, BrF, BrCl） were interaction energies of the complexes oxirane＂.XY and examined by the counterpoise-corrected （CP-corrected） gradient optimization that explicitly corrects the basis set superposition error （BSSE） at the B3LYP/6-311＋＋G（d,p） and B3LYP/aug-cc-pVDZ levels of theory, respectively. The topological properties of halogen-bonded complexes were investigated by the topological analysis of electron density. The nature of halogen bond was investigated, indicating that this kind of halogen bond is between covalent and ionic bonds, with the electrostatic interaction being dominant. The formation of halogen bonds results in an elongation of X--Y bonds, red-shift of vibrational frequencies, which is accompanied by the changes of the integration over atomic basin. The change of bond length, the energy of a halogen bond and the electron density of a critical bond are related to the electronegativity of dihalogen molecules.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2009年第7期593-598,共6页
Acta Chimica Sinica
基金
国家自然科学基金(Nos.20573032
20801017)
河北省自然科学基金(Nos.B2006000137
B2008000138)
河北省教育厅(No.2007123)
河北师范大学青年基金(No.L2007Q18)资助项目.
关键词
分子间相互作用
卤键
B3LYP
电子密度拓扑分析
intermolecular interaction
halogen bond
B3LYP
topological analysis of electron density
