A detailed analysis of the reaction of CH₃CCH₂ and CH₃CHCH with molecular oxygen is presented. The C₃H₅O₂ potential energy surface was characterized using a combination of electronic structure methods. The majority of the stationary points on the PES was determined at the CCSD(T)-F12a/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ level of theory, with the remaining transition states computed using multireference methods. Microcanonical rate theory and the master equation are used to determine the temperature- and pressure-dependent rate coefficients for each reaction channel. The main product channels are CH₂O + CH₃CO for CH₃CCH₂ and CH3CHO + CHO for CH₃CHCH. The rate constants for these two reactions at 1 atm are k = 9.03 × 10²² × T^–3.21 × exp^–2162/T and 1.50 × 10¹⁹ × T^–2.10 × exp^–1260/T cm^–3 mol^–1 s^–1, respectively. In contrast to C₂H₃ + O₂, the methyl-vinyl + O₂ reactions remain chain propagating, even at high temperatures. The new rate coefficients were implemented in a detailed mechanism taken from the literature. These changes have a modest effect on the ignition delay time and laminar flame speeds for propene combustion.

中文翻译：

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甲基-乙烯基+ O ₂反应的理论和计算分析及其对丙烯燃烧的影响

给出了CH ₃ CCH ₂和CH ₃ CHCH与分子氧反应的详细分析。结合电子结构方法对C ₃ H ₅ O ₂势能表面进行了表征。PES上的大多数固定点是在CCSD（T）-F12a / cc-pVTZ-F12 // B2PLYPD3 / cc-pVTZ理论水平上确定的，其余过渡态使用多参考方法计算。微规范速率理论和主方程用于确定每个反应通道的温度和压力相关速率系数。主要产品渠道为CH ₂ O + CH ₃ CO for CH ₃CCH ₂和CH3CHO + CHO表示CH ₃ CHCH。这两个反应在1个大气压下的速率常数分别为k = 9.03×10 ²² × T ^–3.21 ×exp ^{–2162 / T}和1.50×10 ¹⁹ × T ^–2.10 ×exp ^{–1260 / T} cm ^–3 mol ^–1 s ^–分别为¹。与C ₂ H ₃ + O _2相比，甲基乙烯基+ O ₂即使在高温下，反应也会保持链增长。新的速率系数是在从文献中获得的详细机制中实现的。这些变化对点火延迟时间和丙烯燃烧的层流火焰速度影响不大。