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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (10): 899-905. 上一篇    下一篇

研究论文

氧负离子自由基与乙烯反应机理的计算研究

于锋1, 赵英国2, 王勇1, 周晓国*,1, 刘世林1   

  1. (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)
  • 投稿日期:2006-09-30 修回日期:2006-12-11 发布日期:2007-05-28
  • 通讯作者: 周晓国

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

YU Feng1; ZHAO Ying-Guo2; WANG Yong1; ZHOU Xiao-Guo*,1; LIU Shi-Lin1   

  1. (1 Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026)
    (2 Department of Chemistry, Anqing Normal College, Anqing 246011)
  • Received:2006-09-30 Revised:2006-12-11 Published:2007-05-28
  • Contact: Xiao-Guo ZHOU

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被引次数

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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.

关键词: 氧负离子自由基, 乙烯, 反应机理

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.

Key words: atomic oxygen radical anion, ethylene, reaction mechanism