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| CH3SH与NO2的反应机理及动力学 | |
| 引用本文： | 许保恩,李晓艳,曾艳丽,孟令鹏,张萍,刘占荣.CH3SH与NO2的反应机理及动力学[J].化学学报,2009,67(17). |
| 作者姓名： | 许保恩 李晓艳 曾艳丽 孟令鹏 张萍 刘占荣 |
| 作者单位： | 1. 河北师范大学计算量子化学研究所,石家庄,050016;石家庄学院化工学院,石家庄,050035 2. 河北师范大学计算量子化学研究所,石家庄,050016 3. 石家庄学院化工学院,石家庄,050035 |
| 基金项目： | 国家自然科学基金(Nos.20771033,20801017);;河北省自然科学基金(Nos.B2008000141,B2008000138);;河北省教育厅科学研究项目(No.2007123)资助项目 |
| 摘 要： | 在G3B3,CCSD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p)水平上详细研究了CH3SH与基态NO2的微观反应机理.在B3LYP/6-311++G(d,p)水平得到了反应势能面上所有反应物、过渡态和产物的优化构型,通过振动频率分析和内禀反应坐标(IRC)跟踪验证了过渡态与反应物和产物的连接关系.在CCSD(T)/6-311++G(d,p)和G3B3水平计算了各物种的能量,得到了反应势能面.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),分别计算了在200～3000K温度范围内的速率常数kTST,kCVT和kCVT/SCT.研究结果表明,该反应体系共存在5个反应通道,其中N进攻巯基上H原子生成CH3S+HNO2的通道活化势垒较低,为主要反应通道.动力学数据也表明,该通道在200～3000K计算温度范围内占绝对优势,拟合得到的速率常数表达式为k1CVT/SCT=1.93×10-16T0.21exp(-558.2/T)cm3·molecule-1·s-1. |
| 关 键 词： | CH3SH NO2 反应机理 速率常数 |
Reaction Mechanisms and Kinetics for the Reaction of CH3SH+NO2 |
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| Xu Baoen,Li Xiaoyan,Zeng Yanli,Meng Lingpeng,Zhang Ping,Liu Zhanrong.Reaction Mechanisms and Kinetics for the Reaction of CH3SH+NO2[J].Acta Chimica Sinica,2009,67(17). | |
| Authors: | Xu Baoen Li Xiaoyan Zeng Yanli Meng Lingpeng Zhang Ping Liu Zhanrong |
| Institution: | a Institute of Quantum Chemistry;Hebei Normal University;Shijiazhuang 050016;bCollege of Chemical Engineering;Shijiazhuang University;Shijiazhuang 050035 |
| Abstract: | The reaction mechanism of CH3SH with NO2 was investigated by using the density functional theory. The optimum geometries and frequencies of the reactants, transition states and products were com- puted at the B3LYP/6-311++G(d,p) level of theory. Stationary points of the reaction channels were con- firmed by the vibration analysis and the intrinsic reaction coordinate (IRC) tracing. The species energies at all stationary points were corrected by single-point calculations at the G3B3 and CCSD(T)/6-311++G(d,p)... |
| Keywords: | CH3SH NO2 reaction mechanism rate constant |
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