SiH4与HX(X=F,Cl,Br,I)形成的二氢键复合物的结构特征及本质

本文就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，我们确认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2.703－4.439 KJ/mol。用对称匹配微绕理论(SAPT)对结合能进行分解，分解结果显示，SiH4匟X(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匟X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。

Nature and Structural Property of Complexes of Silicane with Hydrogen Halides

The intermolecular complexes of silicane with hydrogen halides are examined using ab initio calculations performed at the second-order Møller-Plesset perturbation approximation with the 6-311++G(3d,3p) basis set. From the geometrical criteria, we think complexes of silicane with hydrogen halides is existence of dihydrogen-bonded. The characteristics of the bond critical points-he electron densities and their laplacians-also confirm this conclusion. The calculated binding energies of complexes of silicane with hydrogen halides using MP2/6-311++G(3d,3p) methods, corrected by basis-set superposition error(BSSE) are 1.703 to 4.439 KJ/mol. In an effort to comprehend the underlying basis of this interaction, we have also carried out a rigorous decomposition of the interaction energies using the symmetry adapted perturbational theory (SAPT) method. The results indicate that the contribution of the electrostatic energies to total attractive energy is less than 28% and relatively stable. This illustrates the nature of dihrdrogen bonds is not electrostatic interaction but electrostatic energies, induction energies, dispersion energies, and ex-change-repulsion energies are all important to the total binding energy.