摘要
采用从头算方法对SiH4与AB型卤素互化物(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.在MP2/6-311++G(3d,3p)水平上优化复合物的分子结构,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与卤素互化物形成反转氢键型复合物.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--9.468kJ·mol-1.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%.
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 MΦller-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. The calculated binding energies of the complexes using MP2/6-311＋＋G（3d,3p） methods and corrected by the basis-set superposition error （BSSE） were-5.113 to-9.468 kJ·mol-1. Decomposition of the interaction energies was carried out using symmetry adapted perturbation theory （SAPT）. The results indicate that the contribution of the induction energy to the total attractive energy ranges from 55.0% to 72.2%, which are the primary contribution to the total attractive energy. The contribution of electrostatic energy and dispersion energy to the total attractive energy are less than 25.0%.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2010年第8期2286-2291,共6页
Acta Physico-Chimica Sinica
基金
贵州省教育厅自然科学研究基金(2008075)
毕节学院科学研究基金(20082006)资助项目~~
关键词
反转氢键
对称匹配微扰理论
SIH4
卤素互化物
Inverse hydrogen bond
Symmetry adapted perturbation theory
Silicane
Interhalogen compound
