SiH4与HX(X=F，Cl，Br，I)形成的二氢键复合物的结构特性及本质  

Nature and Structural Property of Complexes of SiH_4 with HX (X=F, Cl, Br, I)

作　　者：刘红[1] 陈燕芹[1] 王一波 

机构地区：[1]贵州省毕节学院化学系,毕节551700 [2]贵州省高性能计算化学重点实验室,贵阳550025

出　　处：《化学学报》2008年第3期301-307,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20463002);毕节学院科学研究基金(No.20072006)资助项目

摘　　要：对SiH4与HX形成的二氢键复合物的结构特征及本质进行了探讨.在MP2/6-311++G(3d,3p)水平优化、频率验证得到复合物的分子结构,通过分子间距离及电子密度等值线图,确认SiH4与卤化氢已形成了二氢键复合物.MP2/6-311++G(3d,3p)水平下进行BSSE校正后的结合能为2.703～4.439kJ/mol.用对称匹配微扰理论对结合能进行分解,分解结果显示,SiH4…HX(X=F,Cl,Br,I)二氢键复合物中静电能对总吸引能的贡献小于28%,并且相对稳定,这就是说SiH4…HX二氢键复合物的本质并非静电作用,而是静电能、诱导能、色散能、交换能对总结合能的贡献都非常重要.The intermolecular complexes of silicane with hydrohalides were examined using ab initio calculations performed at the second-order MФller-Plesset perturbation approximation with the 6-311 ＋＋ G（3d,3p） basis set. Dihydrogen-bonds were formed in the complexes of silicane with hydrohalides judged from the geometrical criteria. The characteristics of the bond critical points-the electron densities and their Laplacians also confirmed this conclusion. The calculated binding energies of the complexes using MP2/6-311 ＋＋G（3d,3p） methods, corrected by basis-set superposition error, are 1.703 to 4.439 kJ/mol. In an effort to comprehend the underlying basis of this interaction, a rigorous decomposition of the interaction energies was also carried out using the symmetry adapted perturbational theory method. The results indicate that the contribution of the electrostatic energies to the total attractive energy is less than 28% and relatively stable. This illustrates that the nature of dihydrogen bonds is not electrostatic interaction, but the electrostatic energies, induction energies, dispersion energies, and exchange-repulsion energies are all important to the total binding energy.

关 键 词：二氢键 对称性匹配微扰理论 SIH4 卤化氢 本质 

分 类 号：O641.1[理学—物理化学]