A framework for automatic discovery of chemically termolecular reactions
A framework for automatic discovery of chemically termolecular reactions
复制标题
自动发现化学分子反应的框架
DOI：
10.1016/j.proci.2018.05.002
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发表时间：
2019
影响因子：
3.4
通讯作者：
M. P. Burke
中科院分区：
文献类型：
--
作者：
M. Barbet;K. McCullough;M. P. Burke
考虑到在燃烧中遇到的高反应性物质的大摩尔分数，化学反应性碰撞在与负责热化的能量转移碰撞类似的时间尺度上发生的可能性很大。最近的工作表明，这可能导致“化学三分子”反应的重要性燃烧预测。这种类型的反应，其中三个反应物参与键断裂和形成，通常被忽略在以前的唯象动力学模型。组合起来，可能有数百到数千种这样的反应。显然，对所有这些潜在途径进行详细的主方程分析是不可行的，然而，先验地，很难知道这数千个反应中的哪些反应足够可能影响燃烧预测以保证详细的主方程计算。本文提出了一种理论和计算框架，确定和估计潜在的化学三分子反应，其中信息已被限制，基于已知的燃烧机制中的反应的信息的速率常数。本文所述的这种方法在火焰中的应用揭示了一些影响火焰排放和火焰速度的化学三分子反应-包括H + N2+ O = NH + NO、H + CO + H = H2+ CO和H + C2 H2 + O2/OH/H。这些反应，因此，是有价值的候选人详细的主方程计算改进的定量预测。
Given the large mole fractions of highly reactive species encountered in combustion, there is significant potential for chemically reactive collisions to occur on similar timescales as the energy-transferring collisions responsible for thermalization. Recent work has shown that this can result in “chemically termolecular” reactions of importance to combustion predictions. This type of reaction, where three reactants are involved in bond breaking and forming, has generally been neglected in previous phenomenological kinetic models. Combinatorially, there are hundreds to thousands of such reactions that are possible. Clearly, it is not feasible to perform detailed master equation analysis for all of these potential pathways, and yet,a priori, it is difficult to know which of these thousands of reactions are sufficiently likely to impact combustion predictions to warrant detailed master equation calculations. This paper presents a theoretical and computational framework that identifies and estimates rate constants for potential chemically termolecular reactions, for which information has been previously limited, based on information already available for known reactions in combustion mechanisms. Applications of this approach to flames, presented herein, reveal a few chemically termolecular reactions that impact flame emissions and flame speeds – including H + N2+ O = NH + NO, H + CO + H = H2+ CO, and H + C2H2+ O2/OH/H. These reactions, therefore, are worthwhile candidates for detailed master equation calculations for improved quantitative predictions.