【摘要】 在G3MP2B3理论水平下研究了氧负离子自由基(O-)与乙烯(C2H4)的反应机理.计算结果表明,O-与C2H4经碰撞快速复合形成离子诱导偶极络合物中间体,然后经历异构化、解离生成各种产物,分别对应分子离子异构解离与复合电子剥离反应通道.通过比较各个反应途径上势垒的相对高度,发现主要产物通道为复合电子剥离通道,相应的中性产物主要为c-C2H4O;而分子离子解离通道的通道分支比较小,其中生成水反应通道相应的阴离子产物主要是CH2=C-.当前的计算证实了以往实验观察的结论.更多还原

【Abstract】 The reaction mechanism of atomic oxygen radical anion (O-) with ethylene (C2H4) has been in- vestigated at the G3MP2B3 level of theory. The present calculations demonstrate that O- associates quickly with C2H4 to form ion-induced dipole complex, which can subsequently isomerize and decompose to various products, corresponding to molecular anions dissociation and associative electron detachment pathways, re- spectively. Based on the calculated barrier heights for various channels, the main product pathway is the as- sociative electron detachment channel and the corresponding natural product is c-C2H4O; moreover, the branching ratio of molecular anion dissociation channel is smaller, and the main anion product correspond- ing to H2O production channel is CH2=C- anion. The present calculations are consistent with the previous experimental results.更多还原