高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (5): 884.

• 研究论文 • 上一篇    下一篇

H+CH3NO2→H2+CH2NO2反应途径和变分速率常数计算研究

冀永强, 冯文林, 徐振峰   

  1. 北京化工大学理学院, 北京 100029
  • 收稿日期:2001-03-13 出版日期:2002-05-24 发布日期:2002-05-24
  • 通讯作者: 冯文林(1940年出生),男,教授,博士生导师,从事理论化学研究.E-mail:wlfeng@buct.edu.cn E-mail:wlfeng@buct.edu.cn
  • 基金资助:

    国家教育部博士学科点基金(批准号:1999002715);宁夏教育厅高等学校科研基金资助.

Theoretical Study on the Reaction Path and Varitional Rate Constant of Reaction H+CH3NO2→H2+ CH2NO2

JI Yong-Qiang, FENG Wen-Lin, XU Zhen-Feng   

  1. College of Science, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2001-03-13 Online:2002-05-24 Published:2002-05-24

摘要: 采用MP2(FULL)/6-311G**从头算方法,优化了H+CH3NO2——H2+CH2NO2反应的过渡态结构,得出该反应的正逆反应的活化位垒分别是82.73和57.14kJ·mol-1.沿IRC分析指出该反应是一个H—H键生成和C—H键断裂的协同反应,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-0.7~0.2(amu)1/2·a0之间;在1000~1400K温度范围内,运用变分过渡态理论(CVT),计算了该反应的速率常数,计算结果与实验相一致.

关键词: 硝基甲烷, 速率常数, 从头算, 变分过渡态理论

Abstract: Using ab initio theory, the geometries of the reactants, transition state, and products of the reaction H+CH3NO2 H2+CH2NO2 have been optimized at the UMP2(full)/6-31lG** level.The forward and reverse reaction potential barriers are 82.73 and 57.14 kJ/mol respectively.The reaction, that is the formation of H—H bond and breaking of C—H bond, has been shown by a coordination process.Furthermore vibration normal-mode are discussed along the IRC, it is clear that there is a reactivity normal-mode which leads the reaction from reactants to product.The forward reaction theoretical rate constant, obtained by using the variational transition-state theory (CVT), are consistent with experimental value at the reaction temperature 1000—1400 K.

Key words: Nitromethane, Rate constant, Ab initio, Variational transition-state

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