【摘要】 采用二级微扰理论,在MP2(full)/6-311++G(d,p)理论水平上对O(3P)与CH3CFCH2气相反应在三重态势能面上可能的反应机理进行了理论研究,全参数优化了反应过程中反应物、中间体、过渡态和产物等各物种的几何构型,并进行了频率计算.在G3MP2水平上计算了各驻点的能量.计算结果表明,在298.15K下,经过IM2生成CH3+CH2COF产物通道的能垒较低,为主反应通道,而从IM1出发生成H+CH3CFCHO和从IM2出发生成CH2+CH3COF是次要的产物通道.利用经Wigner校正的Eyring过渡态理论计算了在298.15～1500K温度范围内,1个大气压下该反应的速率常数.结果表明,整个反应的速率常数受温度的影响较为复杂.更多还原

【Abstract】 The gas-phase reaction mechanism for the reaction of O(3P) with CH3CFCH2 on the triplet potential energy surface has been investigated with the second-order Mller-Plesset perturbation theory (MP2).The geometries and frequencies of reactants,intermediates,transition states and products have been calculated at the MP2(full)/6-311++G(d,p) level.Single point energies for various species have been calculated at the G3MP2 level.The results indicate that the formation of CH3+CH2COF from IM2 has the lowest barrier height and it is the major product channel,and the products of H+CH3CFCHO from IM1 and CH2+CH3COF from IM2 are the secondary ones. By using the Eyring transition state theory with Wigner correction,the rate constants for the reaction have been given ranging from 298.15 to 1 500 K at standard pressure.The results show that the temperature dependence of rate constants is complicated.更多还原