物理化学学报 >> 2008, Vol. 24 >> Issue (08): 1393-1399.doi: 10.3866/PKU.WHXB20080812

研究论文 上一篇    下一篇

羟基负离子与苯分子的反应机理

王俊霞; 于锋; 刘静; 刘世林; 周晓国   

  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
  • 收稿日期:2008-03-24 修回日期:2008-04-18 发布日期:2008-08-06
  • 通讯作者: 周晓国 E-mail:xzhou@ustc.edu.cn

Reaction Mechanism of Hydroxyl Anion with Benzene

WANG Jun-Xia; YU Feng; LIU Jing; LIU Shi-Lin; ZHOU Xiao-Guo   

  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:2008-03-24 Revised:2008-04-18 Published:2008-08-06
  • Contact: ZHOU Xiao-Guo E-mail:xzhou@ustc.edu.cn

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摘要：

在G3MP2B3理论水平下研究了羟基负离子和苯的反应机理, 系统地分析了该反应体系中可能存在的主要热力学产物通道. 计算结果证实了前人的实验观测结果, 其主要产物是[C6H6…OH]-络合物, 质子转移和置换氢的产物通道为吸热过程, 在较低实验碰撞能量的情况下难以发生, 而生成氢气的反应通道虽然是强放热过程(-119.5 kJ·mol-1), 但其相应的反应能垒较高而无法发生. 计算对比了羟基负离子和氧负离子、氟负离子抽取苯分子中质子的机理所存在的差异, 并结合Mulliken电荷布居分析研究了其中涉及的电子交换过程. 此外, 还对比分析了羟基负离子、羟基自由基与苯反应不同的机理.

关键词: 羟基负离子, 苯, 反应机理

Abstract:

The reaction mechanism of hydroxyl anion and benzene has been theoretically studied at the G3MP2B3 level of theory. All possible thermodynamic product channels are considered and investigated. The [C6H6…OH]- complex formation has been found on the most favorable reaction pathway, which is consistent with the previous experimental studies. The proton transfer and hydrogen replacement pathways are endothermic and difficult to occur in the case of the lower experimental collision energy. Additionally, the H2 formation as an exothermal product channel of this reaction system by -119.5 kJ·mol -1 hardly happens because of a high energy barrier. The proton transfer processes of hydroxyl anion, oxygen anion, and fluorine anion from benzene have been compared in the present computation, and the electron transfers in these processes were investigated by the Mulliken charge population analysis as well. Furthermore, the reaction mechanism between hydroxyl anion or hydroxyl radical and benzene, has been also compared and analyzed.

Key words: Hydroxyl anion, Benzene, Reaction mechanism