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化学学报
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化学学报 ›› 2004, Vol. 62 ›› Issue (6): 550-555. 上一篇    下一篇

研究论文

CH3S与NO基态反应的机理及动力学

王少坤1, 张庆竹1, 周建华2, 顾月姝1   

  1. 1. 山东大学化学与化工学院, 济南, 250100;
    2. 山东轻工业学院化工系, 济南, 250100
  • 投稿日期:2003-08-19 修回日期:2003-11-28 发布日期:2014-02-18
  • 通讯作者: 王少坤,E-mail:wangsk@sdu.edu.cn E-mail:wangsk@sdu.edu.cn
  • 基金资助:
    高等学校博士点专项科研基金(No.1995042201)资助项目.

Theoretical Study on the Gas Phase Reaction of CH3S with NO

WANG Shao-Kun1, ZHANG Qing-Zhu1, ZHOU Jian-Hua2, GU Yue-Shu1   

  1. 1. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100;
    2. Department of Chemical Engineering, Shandong Institute of Light Industry, Jinan 250100
  • Received:2003-08-19 Revised:2003-11-28 Published:2014-02-18

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在G3(MP2)水平上,通过对CH3S与NO反应势能面(PES)上关键驻点的能量计算,共找到3种中间体、7个过渡态、9种产物通道,并对其反应机理进行了讨论.结果表明此反应主要以两种方式进行:一是加成反应,先生成CH3SNO,然后发生单分子解离和异构化反应;二是直接抽提反应,生成CH2S+HNO.用多通道RRKM-TST模型计算了反应随温度和压力变化的速率常数.以295 K的N2作浴气,在200.0～39996.6 Pa压力范围的速率常数为1.6×10-12～1.28×10-11 cm3·molecule-1·s-1.我们计算的速率常数与Balla等的实验值符合较好.反应的速率常数有明显的负温度效应和较强的压力依赖关系.预测常压低温下反应以生成CH3SNO为主,在常压高温1000 K以上以生成CH2S+HNO为主.

关键词: 从头算方法, 甲基硫自由基(CH3S), TSTRRKM理论, 反应机理

A series of key stationary points of potential energy surface (PES) for the CH3S+NO system was calculated at the G3(MP2) level. The calculations reveal three intermediates, seven transition states and nine product channels. With the stationary point energies and TST-RRKM theory, the reaction rates were calculated in the temperature range of 200～1700 K, and the gas phase reaction mechanism of CH3S+NO was discussed. At low temperature, the production of CH3SNO is the main reaction channel. At high temperature, H-abstraction mechanism to give products of CH2S+HNO is the dominant reaction channel, and the other products might be neglected. This result is compared with the experimental value.

Key words: ab initio, methylthiyl, TST-RRKM, reaction mechanism