π-σ轨道作用能分解法和限制π轨道作用的几何优化  

π-σ Energy Partition and Geometry Optimization under the Restrictions of π-Orbital Interactions

作　　者：虞忠衡[1] 包鹏[1] 

机构地区：[1]北京分子科学国家实验室中国科学院化学研究所分子动态稳态国家重点实验室,北京100080

出　　处：《化学进展》2007年第9期1239-1248,共10页Progress in Chemistry

基　　金：国家自然科学基金项目(No.29272070;29572074;29872042;20072041;20272063;20472088;20672119)资助

摘　　要：简要地介绍能量分解法的发展历史,强调能量分解的特点是给量子化学的计算提供明确的化学意义,介绍本实验室建立的能量分解法和限制轨道作用的几何优化法。在这两个方法的基础上,论证了π-电子离域是失稳定的;颠倒了经典有机结构理论中基本的因果关系——共轭效应和构象之间的因果关系;为芳香能的计算提供了一个新的模型和新的方法,表明芳香能的计算不再需要参考分子;定量地区别静电作用和电子离域在化学键形成中的作用;定量地讨论取代基效应和张力芳环的扭曲驱动力。The history of energy partition is reviewed. It is emphasized that the energy partition is to provide quantum calculation with the chemical meanings. The new methods of energy partition and geometry optimization under restrictions of orbital interactions are introduced, and these are developed in our research group. Based on these two methods, the viewpoint that π-electron delocalization is destabilization has been brought forward. The fundamental causality of classical organic structure theory, a relationship between resonance and molecular conformation, seems to be overturns, and it is confirmed that π-π and σ-σ orbital interactions are the driving forces for distorting NBA away from its planar geometry. A new quantitative method for evaluating aromaticity energy is developed, indicating that the reference molecule （or molecules） is no longer necessary for calculating stabilizing energy for aromatic molecule. The roles of electrostatic interaction and electron delocalization in forming chemical bond are distinguished quantitatively. Substitutent effects and driving forces for distorting strained cyclic molecules are discussed.

关 键 词：能量分解 限制轨道作用 几何优化 电子离域 芳香性 取代基效应 环张力 

分 类 号：O621.13[理学—有机化学]