氧负离子自由基与乙烯反应机理的计算研究  

Computational Investigation on the Reaction Mechanism of Atomic Oxygen Radical Anion with Ethylene

作　　者：于锋[1] 赵英国[2] 王勇[1] 周晓国[1] 刘世林[1] 

机构地区：[1]中国科学技术大学化学物理系合肥微尺度物质科学国家实验室(筹),合肥230026 [2]安庆师范学院化学系,安庆246011

出　　处：《化学学报》2007年第10期899-905,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20533070;20603033);安徽省自然科学基金(No.070415214)资助项目.

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.The reaction mechanism of atomic oxygen radical anion （O^-） with ethylene （C2H4） has been investigated 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, respectively. Based on the calculated barrier heights for various channels, the main product pathway is the associative 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 corresponding to H2O production channel is CH2 = C^- anion. The present calculations are consistent with the previous experimental results.

关 键 词：氧负离子自由基 乙烯 反应机理 

分 类 号：O643.12[理学—物理化学]