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用直接从头算动态学方法对CH2N+HONO→CH2NH+NO2反应进行了研究.用BH&HLYP/6-31+G(d,p)方法对所有稳定结构和过渡态的几何结构进行了优化,并用内禀反应坐标方法计算了最小能量路径(MEP.)在QCISD(T/)6-311+G(2df,2pd)理论水平上对所有结构的能量进行了进一步校正.用变分过渡态理论(CVT)在考虑小曲率隧道(SCT)校正的水平上计算了200￣2500 K温度范围内标题反应的热速率常数.计算结果表明,上述温度范围内热速率常数有正的温度效应,计算结果与文献数据能够很好地吻合.
The reaction of CH2N + HONO → CH2NH + NO2 has been studied by the direct ab initio kinetic method, and the geometry of all stable and transition states has been optimized using the BH & HLYP / 6-31 + G (d, p) In the intrinsic reaction coordinate method, the minimum energy path (MEP) is calculated to further correct the energy of all structures at the theoretical level of QCISD (T /) 6-311 + G (2df, 2pd) ) Calculated the thermal rate constant of the title reaction in the temperature range of 200 ~ 2500 K on the basis of the SCT correction. The calculated results show that the thermal rate constant in the above temperature range has a positive temperature effect. The calculation results are in good agreement with the literature data Can fit well.