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本文用量子化学(简称量化)的半经验及从头算法对氨基乙烯及乙烯与单线态氧1,2-加成反应机理进行了研究。首先应用MINDO/3辅以Powell法对两个体系各基元过程过渡态进行了优化。得到了与前人不同的结构。而后利用Fukui提出的IRC理论计算了这两个体系整个反应途径。计算结果不但证实我们所得过渡态结构的可靠性,也证实对于富电子烯烃,反应确实经由两性离子中间体。同时基于反应途径对反应全过程进行了详细分析并结合从头算相互作用能的分解对取代基电子效应提出了较为深入合理的理论解释。
In this paper, the semi-empirical and ab initio quantum chemical (abbreviated quantification) 1,2-addition reaction mechanism of ethylene and singlet oxygen has been studied. Firstly, MINDO / 3 and Powell method were used to optimize the transition state of each elementary process of the two systems. Got a different structure with their predecessors. Then the IRC theory proposed by Fukui was used to calculate the whole reaction pathway of these two systems. The calculated results not only confirm the reliability of the transition state structure we obtained, but also confirm that for the electron rich olefins, the reaction does indeed proceed through the zwitterionic intermediate. At the same time, the detailed analysis of the reaction process based on the reaction pathway and the decomposition of the ab initio interaction energy have provided a more in-depth and reasonable theoretical explanation for the substituent electron effect.