Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551-0969, USA.
J Phys Chem A. 2010 Apr 15;114(14):4881-90. doi: 10.1021/jp910604b.
This article describes a detailed theoretical analysis of the reaction between allyl and propargyl. In this analysis, we employ high-level electronic structure calculations to characterize the potential energy surface and various forms of transition-state theory (TST) to calculate microcanonical, J-resolved rate coefficients-conventional TST for isomerizations, and the variable reaction coordinate form of variational TST for the "barrierless" association/dissociation processes. These rate coefficients are used in a time-dependent, multiple-well master equation to determine phenomenological rate coefficients, k(T,p), for various product channels. The analysis indicates that the formation of (cyclic) c-C(6)H(7) and c-C(6)H(8) species is suppressed by elevated pressure. Overall, the results suggest that the formation of these five-membered rings from the reaction is not as important as previously thought. A simplified description of the kinetics of the reaction is discussed, and corresponding rate coefficients are provided.
本文详细地分析了烯丙基与丙炔基的反应。在分析中，我们采用高精度的电子结构计算来描述势能面，并采用多种过渡态理论（TST）形式来计算微观正则、J 分辨速率系数——对构象变化的传统 TST 和对“无阻”缔合/解离过程的变分 TST。这些速率系数被用于含时、多势阱的主方程中，以确定各种产物通道的唯象速率系数 k(T,p)。分析表明，高压会抑制（环状）c-C(6)H(7)和 c-C(6)H(8)物种的形成。总体而言，结果表明这些五元环的形成并不像之前认为的那样重要。文中还讨论了反应动力学的简化描述，并提供了相应的速率系数。
