物理化学学报 >> 2011, Vol. 27 >> Issue (03): 564-570.doi: 10.3866/PKU.WHXB20110308

理论与计算化学 上一篇    下一篇

HOSO+NO反应的机理及动力学

李晓艳, 刘群, 郑世钧, 孟令鹏   

  1. 河北师范大学化学与材料科学学院, 石家庄 050016
  • 收稿日期:2010-09-20 修回日期:2010-12-07 发布日期:2011-03-03
  • 通讯作者: 孟令鹏 E-mail:menglp@mail.hebtu.edu.cn
  • 基金资助:

    国家自然科学基金(20973053, 20771033, 20801017), 河北省自然科学基金(B2010000371, B2011205058), 河北省教育厅基金(2009137)和河北师范大学基金(L2008B06, L2009Y06)资助项目

Mechanisms and Kinetics of the HOSO+NO Reaction

LI Xiao-Yan, LIU Qun, ZHENG Shi-Jun, MENG Ling-Peng   

  1. College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050016, P. R. China
  • Received:2010-09-20 Revised:2010-12-07 Published:2011-03-03
  • Contact: MENG Ling-Peng E-mail:menglp@mail.hebtu.edu.cn
  • Supported by:

    The project was supported by the the National Natural Science Foundation of China (20973053, 20771033, 20801017), Natural Science Foundation of Hebei Province, China (B2010000371, B2011205058), Education Department Foundation of Hebei Province, China (2009137), and Foundation of Hebei Normal Univeristy, China (L2008B06, L2009Y06).

摘要:

在B3LYP/6-311++G(d,p)水平上研究了HOSO+NO的反应机理. 优化得到了反应势能面上各驻点的几何构型, 通过内禀反应坐标(IRC)确认了反应物、中间体、过渡态和产物的相关性. 在CCSD(T)/6-311++G(d,p)水平上对计算得到的构型进行了能量校正. 应用经典过渡态理论(TST)与变分过渡态理论(CVT), 并结合小曲率隧道(SCT)效应模型校正的方法计算了标题反应在200-3000 K温度范围内的速率常数kTST、kCVT和kCVT/SCT. 计算结果表明: HOSO+NO反应在单重态和三重态条件下均可发生, 其中单重态反应为主反应通道, HNO+SO2为主产物. 并利用电子密度拓扑分析方法研究主反应通道反应过程中的化学键变化.

关键词: HOSO, 反应机理, 速率常数, 电子密度拓扑分析

Abstract:

The mechanism of the reaction between HOSO and NO was investigated at the B3LYP/6-311++G(d,p) level of theory. The geometries of the reactants, intermediates, transition states, and products were optimized. The intrinsic reaction coordinates (IRC) were traced and the connecting relationship between the transition states and the reactants, products were confirmed. The single point energies of the species were corrected at the CCSD(T) /6-311++G(d,p) level of theory. The reaction rate constants were calculated over a temperature range of 200-3000 K using classical transition state theory (TST) and canonical vibration transition state theory (CVT) combined with a small-curvature tunneling (SCT) correction. The results showed that the HOSO+NO reaction occurs in both the singlet and triplet reaction channels. The singlet reaction channel is dominant, and HNO and SO2 are the main products. The chemical bond changes in the main reaction channel were analyzed by a topological analysis of the electron density.

Key words: HOSO, Reaction mechanism, Rate constant, Topological analysis of electron density

MSC2000: 

  • O641