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化学学报
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化学学报 ›› 2003, Vol. 61 ›› Issue (10): 1577-1581. 上一篇    下一篇

研究论文

过亚硝酸异构化反应机理的密度泛函理论研究

王辉宪;彭清静;罗明道$D曾跃   

  1. 湖南农业大学理学院应用化学系;吉首大学生物资源与环境科学学院化学系;武汉大学化学与分子科学学院$D湖南师范大学化学化工学院
  • 发布日期:2003-10-15

Study on the Isomerization Mechanism of ONOOH by DFT

Wang Huixian;Peng Qingjing;Luo Mindao;Zeng Yue   

  1. Department of Chemistry, Jishou University;College of Chemistry and Molecular Sciences, Wuhan University;College of Chemistry, Hunan Normal University
  • Published:2003-10-15

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被引次数

9 | 5

用密度泛函理论方法研究了过亚硝酸在水溶液中的异构化反应机理。在 B3LYP/6-31G水平基础上用梯度解析技术全自由度优化了反应物、产物和反应途径 中的中间产物及过渡态的几何构型，并通过振动频率分析加以确认，进行了内禀反 应坐标计算，确定了该反应的可能通道。结果表明：该反应为多通道强放热反应， 其中以羟基直接转移途经能垒最小，绝对反应速率常数值最大，因此，推测该通道 为主要的反应通道。

关键词: 密度泛函理论, 过亚硝酸, 异构化, 反应机理, 构型

The isomerization mechanism of peroxynitrous acid (ONOOH) in the aqueous solution has been studied by using density function theory. The geometries of reactants, transition states, intermediates and products have been optimized by B3LYP/6-31G(d) basis set and verified by frequency analysis. The reaction pathway was traced by Fukui's theory of intrinsic reaction coordinate (IRC) . The reaction channels were verified. The study shows thai the isomerization reaction is a multi-step and multi-channel complex one, and highly exothermic. Among them the channel (1) is a principal one. The activation energy is 129. 9 kJ/mol. The absolute rate constant is 1.95 * 10~(-10)s ~(-1).

Key words: DFT, ONOOH, ISOMERIZATION, REACTION MECHANISM, CONFIGURATION

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