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O(^3P)+CH3CF=CH2气相反应动力学的理论研究 被引量:1

Kinetic study of gas-phase reaction of O ( ^3 p) with CH3 CF=CH2
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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. The gas-phase reaction mechanism for the reaction of O(^3P) with CH3 CF=CH2 on the triplet potential energy surface has been investigated with the second-order Moller-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.
作者 杜本妮
出处 《徐州师范大学学报(自然科学版)》 CAS 2009年第2期78-83,共6页 Journal of Xuzhou Normal University(Natural Science Edition)
基金 徐州师范大学自然科学基金资助项目(07XLB09)
关键词 O(3P) CH3CFCH2 G3MP2 反应机理 反应速率常数 O(^3P) CH3CF=CH2 G3MP2 reaction mechanism reaction rate constant
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参考文献25

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