【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57．14 kJ·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 1000～1400 K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．更多还原

【Abstract】 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桯 bond and breaking of C桯 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 1 000? 400 K.更多还原