SiH4与AB型卤素互化物之间的反转氢键.PDFVIP

理化学学报(Wuli Huaxue Xuebao) 2286 A cta Phys. Chim. Sin., 2010, 26(8) ：2286-2291 August [Article] SiH4 AB 型卤素互化物之间的反转氢键 红 陈燕芹 杨玉琼 (毕节学院化学系, 贵州毕节 551700) 摘要： 采用从头算方法对SiH4 与AB 型卤素互化 (ClF、BrF 、IF、ICl、IBr、BrCl)形成的复合物的结构特征及本 质进行了探讨援 在MP2/6 311++G(3d,3p )水平上优化复合 的分子结构, 并进行频率验证. 通过分子间距离、自然 键轨道(NBO)净电荷迁移数及分子图, 确认SiH4 与卤素互化 形成反转氢键型复合 援 在MP2/6 311++G(3d,3p ) 水平上进行基组重叠误差(BSSE)校正后的作用能为-5.113 - -9.468 kJ ·mol-1援 用对称匹配微扰理论(SAPT)对作 用能进行分解, 结果显示, 诱导能对总吸引能的贡献在55.0%到72.2%之间, 是最主要的贡献部分, 静电能和色散 能对总吸引能的贡献都小于25.0%. 关键词： 反转氢键; 对称匹配微扰理论; SiH ; 卤素互化 4 中图分类号： O641 Inverse Hydrogen Bond between Silicane and AB Type Interhalogen Compounds LIU Hong CHEN Yan Qin YANG Yu Qiong (Dep artment of Chemistry, Bijie University, Bijie 551700, Guizhou Province, P. R. China) Abstract ： Intermolecular complexes of silicane with AB type interhalogen compounds (ClF, BrF, IF, ICl, IBr, BrCl) were examined using ab initio calculations performed at the second order M覬ller Plesset perturbation approximation with the 6 311++G(3d ,3p ) basis set . Frequency calculations were also run using the same level of theory . Inverse hydrogen bonds were formed in the complexes of silicane with AB type interhalogen compounds as determined by the geometrical criteria and the natural bond orbital (NBO) net charge transfer number as well as the molecular graphs. T