【摘要】 在G2(B3LYP/MP2/CC)理论水平上研究了CH3自由基与一氧化氮分子(NO)的反应.计算了反应体系最低势能面上各驻点的构型参数、振动频率和能量,全面研究了此反应的反应机理及各个可能的反应通道;利用多通道TST RRKM理论计算了300～2500K的总包反应速率常数的温度效应、压力效应和各反应通道的分支比.详细讨论了活化分子碰撞失活对反应速率的贡献,计算结果和实验数据符合得较好.更多还原

【Abstract】 The reaction mechanism of CH₃ radical with NO was investigated at G2（B3LYP/MP2/CC） level. The equilibrium geometries, harmonic frequencies and energies of various stationary points on the potential energy surfaces have been calculated in the lowest singlet states. Various possible reaction pathways and reaction mechanism were probed in details. Transition-State-RRKM theory calculations for the reaction successfully describe the temperature and pressure dependences. The branching ration is calculated in the range of 300-2500 K. The contribution of stabilization of adducts to the reaction rate constant was discussed. The calculations provide a well consistent description for the previous experimental work.更多还原