201012013-刘红-2试题.doc

·研究论文· GeH4与HXXF,Cl,Br间二氢键复合物的理论研究 刘红* 陈燕芹 贵州省毕节学院化学系 毕节 551700摘要 对GeH4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++G3d,3p水平优化、频率验证得到复合物的分子结构，通过分子及电子密度拓扑分析，确认GeH4与卤化氢已形成了二氢键复合物．MP2/6-311++G3d,3p水平下进行BSSE校正后的结合能为3.281到4.502 kJ·mol．．分子间超共轭作用与静电吸引作用产生的红移效应超过重极化和重杂化产生的蓝移效应H5-X键红移负重极化及负重杂化与H Ge和H X的静电吸引作用一致导致Ge –H键拉长与振动频率红移． 关键词 二氢键；；；GeH4；卤化氢[中图分类号] 　O 641 　　　[学科代码] 　150·30 　　　[文献标识码] 　A Theoretical Study on dihydrogen bond of GeH4 with HXXF, Cl,BrLIU, Hong CHEN, Yan-QinDepartment of Chemistry, Bijie University, Bijie 551700, Guizhou Province, P. R. China Abstract The intermolecular complexes of GeH4 with hydrohalides were examined using ab initio calculations performed at the second-order M?ller-Plesset perturbation approximation with the 6-311++G3d,3p basis set. Dihydrogen-bonds were formed in the complexes of GeH4 with hydrohalides judged from the geometrical criteria. The characteristics of the bond critical points—the electron densities and their laplacians—also confirm this conclusion. The calculated binding energies of the complexes using MP2/6-311++G3d,3p methods, corrected by basis-set superposition error are 3.28 to 4.502 kJ·mol-1. The analysis of natural bond orbital shows that the electrostatic interaction plays a role in the formation of dihydrogen-bonds. For H5-X bond, the red shift caused by intremolecular hyperconjugation and electrostatic attraction is greater than blue shift caused by repolarization and rehybridization, resulting in red shift of H5-X bond. For Ge-H bond, negative repolarization and negative rehybridization are consistent with the electrostatic attraction, resulting in Ge-H4 bond stretching and vibration frequency red shift. Keywords dihydrogen bonding; AIM; NBO;GeH4; hydrogen halides收稿日期：2010-12-20 基金项目： 贵州省教育厅自然科学研究基金（座机电话号码）及毕节学院科学研究基金（座机电话号码）资助项目 联系人简介：刘红1980- ,男,硕士,副教授,主要从事应用量子化学及光谱学研究. Email: hliu315@126.com 氢键广泛存在于物理、化学和生物等体系中，它在分子识别，超分子组装等方面都有重要的应用[1]．由于分子间相互作用在生命科学和材料科学中的重要作用，因此对其作用机制、作用本质的理论研究都具有十分重要的意义[]．经典氢键以X-H…Y表示