物理化学学报 >> 2006, Vol. 22 >> Issue (09): 1095-1100.doi: 10.1016/S1872-1508(06)60050-8

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氧负离子自由基与苯的反应机理研究

赵英国;周晓国;于锋;戴静华;刘世林   

  1. (合肥微尺度物质科学国家实验室(筹), 中国科技大学化学物理系, 合肥 230026)
  • 收稿日期:2006-03-27 修回日期:2006-04-14 发布日期:2006-09-04
  • 通讯作者: 周晓国 E-mail:xzhou@ustc.edu.cn

Investigation of the Mechanism of the Reaction between Atomic Oxygen Radical Anion and Benzene

ZHAO Ying-Guo;ZHOU Xiao-Guo;YU Feng;DAI Jing-Hua;LIU Shi-Lin   

  1. (Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China)
  • Received:2006-03-27 Revised:2006-04-14 Published:2006-09-04
  • Contact: ZHOU Xiao-Guo E-mail:xzhou@ustc.edu.cn

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摘要： 采用密度泛函理论研究了氧负离子自由基与苯分子的反应. 针对可能存在的抽氢反应、置换氢反应、生成水反应及羟基化反应通道, 在B3LYP/6-31+G(d, p)的水平上得到了反应物、产物、中间体复合物和过渡态的优化构型、振动频率以及能量, 证实了这个反应的多产物通道性质, 较完整地描述了反应的机理和产物生成途径. 并且利用G2MP2能量计算结果, 从反应途径的能垒高度定性说明了实验观测结果的合理性, 同时也解释了以往实验的矛盾结果.

关键词: 氧负离子自由基, 苯, 反应机理

Abstract: The reaction mechanism between atomic oxygen radical anion and benzene has been investigated using the density functional theory (DFT). Geometries of the reactants, products, complexes and transition states involved have been optimized at the B3LYP/6-31+G(d, p) level, and their vibrational frequencies and zero-point energies (ZPEs) have been calculated subsequently at the same level. The multichannel pathways, e.g. the H-atom abstraction, oxide-ion formation, H2+ transfer, and proton transfer, are confirmed by calculated potential energy surface of this reaction described in this study. Based on the G2MP2 energies, a reasonable description has been proposed qualitatively to explain the inconsistency of previous experimental conclusions.

Key words: Atomic oxygen radical anion, Benzene, Reaction Mechanism