CH_2N+HONO反应的动力学研究  

A Dynamics Study on the Reaction of CH_2N+HONO

作　　者：邢静[1] 申家凤[1] 张绍文[1] 张云霄[2] 

机构地区：[1]北京理工大学理学院化学系,北京100081 [2]石家庄学院化学系,河北石家庄050035

出　　处：《石家庄学院学报》2005年第6期1-4,共4页Journal of Shijiazhuang University

基　　金：国家自然科学基金(项目号:20373007)

摘　　要：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.This paper presents an ab initio direct dynamics study of thermal rate constants of the hydrogen abstraction reaction of CH2N＋HONOCH2NH＋NO2.Bhandhylp/6-31＋g（d,p） methods were employed to optimize the geometries of all stationary points and to calculate the minimum energy path（MEP）.The energies of all the points were further refined at the QCISD （T）/6-311＋G （2df,2pd）level of theory.The thermal rate constants of the title reaction were calculated using canonical variational transition state theory （CVT） and canonical variational transition state theory with small curvature tunneling contributions （CVT/SCT） in the temperature range of 200-2500 K.The calculated results show that the rate constants have positive temperature dependence in the calculated temperature range.

关 键 词：从头算法 速率常数 变分过渡态理论 隧道效应 

分 类 号：O641.12[理学—物理化学]