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在G3MP2B3理论水平下研究了氧负离子与乙烯自由基的反应机理.反应入口势能面的刚性扫描显示:对于不同的初始反应取向,体系存在3种不同的反应机理,分别对应直接脱水、插入反应和直接键合成中间体通道.其中,通过插入反应形成的富能中间体[CH2=C—OH]-及键合中间体[CH2=CHO]-都可以进一步经异构化和解离生成其它各种可能产物,如C2H-+H2O,OH-+CH2C和CH3-+CO产物通道.基于计算得到的反应势垒的相对高度,直接脱水反应显然是该反应体系最主要的产物通道,同时我们还结合Mulliken电荷布居分析研究了其中涉及的电子交换过程.由此,计算结果证实了以往OH-与C2H2反应的实验研究结果.此外,还对比了该反应体系、氧原子与乙烯自由基、氧负离子与乙烯分子三个反应的不同机理.
The reaction mechanism of oxygen anion and ethylene radical has been studied at the theoretical level of G3MP2B3.The rigid scanning of the potential energy surface of the reaction inlet shows that there are three different reaction mechanisms for the different initial reaction orientations, corresponding to the direct dehydration, the insertion reaction and Directly bond to the intermediate channel, wherein the energy-rich intermediate [CH2 = C-OH] - and the bonding intermediate [CH2 = CHO] - formed by the insertion reaction can be further isomerized and dissociated to generate other various Possible products, such as C2H- + H2O, OH- + CH2C and CH3- + CO product channels.Based on the calculated relative height of the reaction barrier, the direct dehydration reaction is obviously the most important product channel for the reaction system, and we also combine Mulliken charge population analysis of the electronic exchange process involved in which the calculation results confirm the previous OH- and C2H2 reaction experimental results.In addition, compared the reaction system, oxygen atoms and ethylene radicals, oxygen anions Different mechanism of reaction with three ethylene molecules.