氧负离子自由基与苯的反应机理研究.pdfVIP

理化学学报(Wuli Huaxue Xuebao) September A cta Phys. Chim. Sin., 2006, 22(9) ：1095 1100 1095 [Article] 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 (合肥微尺度 质科学国家实验室(筹), 中国科技大学化学 理系, 合肥 230026) 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鄄31+G(d, p ) 的水平上得到了反应 、产 、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 通道性质, 较完整地描述了反应的机理和产 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 中图分类号： O641 Investigation of the Mechanism of the Reaction between Atomic Oxygen Radical Anion and Benzene ZHAO, Ying鄄Guo ZHOU, Xiao鄄Guo YU, Feng DAI, Jing鄄Hua LIU, Shi鄄Lin (Hef ei National Laboratory f or Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hef ei 230026, P. R. China) 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鄄31+G(d, p ) level, and their vibrational frequencies and zero鄄point energies (ZPEs) have been calculated subsequently at the same level. The multichannel pathways, e.g. the H鄄atom abstraction, oxide鄄 ion formation, H + transfer, and proton transfer, are confirmed by calculated potential energy surface of this reaction 2 described in this study. Based