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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (17): 1957-1964.    下一篇

研究论文

过氧氢自由基HO2与CH2S的反应机理及动力学

刘占荣1,2，许保恩1,2，曾艳丽1，李晓艳1，孟令鹏*,1，孙政1，张雪英1，张萍2   

  1. (1河北师范大学计算量子化学研究所 石家庄 050016)
    (2石家庄学院化工学院 石家庄 050035)
  • 投稿日期:2010-12-23 修回日期:2011-04-12 发布日期:2011-05-11
  • 通讯作者: 孟令鹏 E-mail:menglp@mail.hebtu.edu.cn
  • 基金资助:

    AIM和ELF理论方法及应用的新拓展;取代元素对镁基储氢合金结构和性质影响的理论研究;电子密度拓扑分析理论方法研究弱键结构;金属氢化物储氢材料的结构、成键作用及稳定性的理论研究;用电子密度拓扑分析理论研究有机金属簇合物中的化学键;大气化学中光化学氧化剂的反应活性研究;镁基储氢合金结构、性质及储氢机制的理论研究

Reaction Mechanisms and Kinetics for the Reaction of HO2＋CH2S

Liu Zhanrong1,2 Xu Baoen1,2 Zeng Yanli1 Li Xiaoyan1 Meng Lingpeng*,1 Sun Zheng1 Zhang Xueying1 Zhang Ping2   

  1. (1 Institute of Quantum Chemistry, Hebei Normal University, Shijiazhuang 050016)
    (2 College of Chemical Engineering, Shijiazhuang University, Shijiazhuang 050035)
  • Received:2010-12-23 Revised:2011-04-12 Published:2011-05-11

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采用密度泛函理论B3LYP方法, 在6-311＋＋G(d,p)基组水平研究了HO2与CH2S的微观反应机理. 在CCSD(T)/6-311＋＋G(d,p)//B3LYP/6-311＋＋G(d,p)水平上获得了势能面. 利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT), 计算了反应通道在200～2500 K温度范围内的速率常数kTST, kCVT和kCVT/SCT. 找到了该反应体系的6个反应通道, 其中HO2的端位O进攻CH2S中C生成的HOOCH2S及其异构化得到的OOCH2SH均为主反应产物. 动力学数据也表明, 当温度低于1400 K时, 通道(1a) HO2＋CH2S→TS1/P1→HOOCH2S是主反应通道, 高于1400 K时, 通道(2a) HO2＋CH2S→ TS2/P1 → HOOCH2S占优势.

关键词: HO2, CH2S, 反应机理, 速率常数

The reaction mechanism of HO2 with CH2S was investigated at the B3LYP/6-311＋＋G(d,p) level. Energetic information of stationary points and the points along the minimum energy path is further refined at the CCSD(T)/6-311＋＋G(d,p) level. The rate constants of these channels in the temperature range of 200～2500 K were evaluated by means of the classical transition state theory (TST) and the canonical variational transition state theory (CVT) conjunction with the small-curvature tunneling correction (SCT). Six possible reaction channels have been identified for the title reaction. Based on the potential energy surface and the kinetics, it can be concluded that HOOCH2S, formed via the end O atom of the HO2 radical attacking on the C atom of the CH2S molecule, and its isomer OOCH2SH are the major products. When the temperature is lower than 1400 K, the channel (1a) HO2＋CH2S→TS1/P1→HOOCH2S is the major reaction path, while the channel (2a) HO2＋CH2S→TS2/P1→HOOCH2S becomes the favorable reaction path when the temperature is higher than 1400 K.

Key words: HO2, CH2S, reaction mechanism, rate constant

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