| CH3NO2和CH3自由基吸氢反应途径和变分速率常数计算 |
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| 引用本文： | 冀永强,冯文林,郝茂荣,李会英. CH3NO2和CH3自由基吸氢反应途径和变分速率常数计算[J]. 物理化学学报, 2002, 18(8): 721-726. DOI: 10.3866/PKU.WHXB20020810 |
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| 作者姓名： | 冀永强 冯文林 郝茂荣 李会英 |
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| 作者单位： | Faculty of Science, Beijing University of Chemical Technology, Beijing 100029 |
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| 基金项目： | 高等学校博士点专项科研基金(1999002715)，宁夏教育厅资助项目 |
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| 摘 要： | 采用MP2(full)/6-311G(d, p)从头算方法,优化了硝基甲烷和甲基自由基吸氢反应的过渡态结构,经QCISD(T)方法进行能量校正,得出该反应的正逆向反应的活化位垒分别是58.21 kJ•mol－1和67.17 kJ•mol－1.沿IRC分析指出该反应是氢转移协同反应,而且在反应途径上存在一个引导反应进行的振动模式,这一反应模式引导反应进行的区间在反应坐标S的-0.9～1.0(amu)1/2bohr之间;在温度为800～2600 K范围内,运用改进的变分过渡态理论(ICVT),计算了该反应的速率常数,并与实验类比所得的速率常数随温度的变化趋势进行了比较.
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| 关 键 词： | 硝基甲烷 速率常数 从头算 变分过渡态理论 |
| 收稿时间： | 2001-12-04 |
| 修稿时间： | 2002-03-19 |
The Reaction Path and Varitional Rate Constant of the Reaction CH3＋CH3NO2→CH4＋CH2NO2 |
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| Ji Yong-Qiang Feng Wen-Lin Hao Mao-R ong Li Hui-Ying. The Reaction Path and Varitional Rate Constant of the Reaction CH3＋CH3NO2→CH4＋CH2NO2[J]. Acta Physico-Chimica Sinica, 2002, 18(8): 721-726. DOI: 10.3866/PKU.WHXB20020810 |
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| Authors: | Ji Yong-Qiang Feng Wen-Lin Hao Mao-R ong Li Hui-Ying |
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| Affiliation: | Faculty of Science, Beijing University of Chemical Technology, Beijing 100029 |
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| Abstract: | The geometries of the reactants, transition state, and products of hydrogen transfer reaction CH3＋CH3NO2→CH4＋CH2NO2 have been optimized at the UMP2(full)/6-311G(d, p) level. The forward and reverse reaction potential barriers are 58.21 kJ•mol－1 and 67.17 kJ•mol－1 respectively. Along the IRC, the reaction is a coordinative process and there is a reactivity normal-mode, which lead reaction from reactants to product. The variation of forward reaction rate constant versus temperature, obtained by using the variation transition-state theory (CVT) and ICVT, have identical tendency with experimental values. |
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| Keywords: | Nitromethane Rate constant Ab initio Variation transition-state theory |
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