类铝烯HAlLiX(X=F,Cl)的构型及异构化反应的量子化学研究

Quantum Chemistry Study on the Geometries and Isomerizations for HAlLiX(X=F,Cl) Fragment *

用ＲＨＦ／６－３１Ｇ＊解析梯度方法研究了类铝烯ＨＡｌＬｉＦ和ＨＡｌＬｉＣｌ的结构。均得到了４个平衡构型和３个异构化反应的过渡态构型。经动力学分析表明，其中各自的两种平衡构型是它们存在和参加化学反应的基本构型。文中分析了各平衡构型的结构特点及稳定性，给出了各构型的Ｍｕｌｉｋｅｎ集居数和基本平衡构型的前线分子轨道，并讨论了基本平衡构型的反应活性及卤素原子（Ｆ，Ｃｌ）对构型稳定性和反应活性的影响。

Structures of the fragments HAlLiF and HAlLiCl have been investigated by ab initio method at RHF/6-31G* level,generating four equilibrium geometries for each fragment and three transition states regarding isomerization reactions between the four geometries.The kinetic analysis indicates that both HAlLiF and HAlLiCl exist and take part in chemical reactions in the two basic geometries.The characteristics and stability of the involved equilibrium geometries are analyzed.The Mulliken populations of the involved geometries and the frontier molecular orbitals of the two basic geometries were given.Moreover,the chemical activities of the basic geometries,and effects of the halogen atoms (F,Cl) on the geometry stability and the chemical activities of the basic geometries have also been discussed.