Theoretical Studies on the reaction control and the molecular design for the ground and excited states of electrocyclic reactions

用理论方法研究了四个项目的周循环反应。(1)苯基对1,5-己二烯Cope重排的取代作用。从我们的计算结果来看，Cope重排分为两种类型：通过芳香过渡态的协同反应和带有中间体的双自由基路径的协同反应。(2)对两个乙烯的循环反应机理进行了CiLC- IRC分析。采用CiLC-IRC法分析了两个乙烯循环反应的两种反应机理，即超反应和反反应。这两种反应机制都是通过突然极化态发生的，并受两轨道重叠的控制。(3) 1,3-偶极反应机理的CiLC-IRC分析。用从头算MO方法研究了1,3-偶极反应的反应机理。双键部分的活化能与双基型的离解能有关。(4)分子动力学中包含溶剂效应的分子轨道方法的发展。提出了一种新的分子动力学分子轨道方法。

Four projects as peri-cyclic reactions were investigated by theoretical methods.(1) The substitution effects of phenyl group for the Cope rearrangements of 1,5-hexadiene. From our calculation results, the Cope rearrangement is classified into two types: concerted reaction through the transition state with aromaticity and bi-radical path with intermediate.(2) The CiLC- IRC analysis for the reaction mechanisms of cyclic reactions of two ethylene. The two reaction mechanisms, supra and antara, for cyclic reaction of two ethylene were analyzed by the CiLC-IRC method. The both reaction mechanisms occur through the sudden polarized states, and are in the control of overlap between both orbitals.(3) The CiLC-IRC analysis for the reaction mechanisms of 1,3-Dipolar reactions. The reaction mechanisms of 1,3-Dipolar reaction were investigated by ab initio MO methods. The activation energies are govern with the dissociation energies of bi-radical type for double bond part.(4) The development of the molecular orbital methods including solvent effects for the molecular dynamics. New molecular orbital method (IMiC MO) for molecular dynamics were presented.