Understanding and Representing the Distinct Kinetics Induced by Reactive Collisions of Rovibrationally Excited Ephemeral Complexes across Reactive Collider Mole Fractions and Pressures
Understanding and Representing the Distinct Kinetics Induced by Reactive Collisions of Rovibrationally Excited Ephemeral Complexes across Reactive Collider Mole Fractions and Pressures
复制标题
理解和表示由旋转激发的短暂复合物在反应对撞机摩尔分数和压力上的反应碰撞引起的独特动力学
DOI：
10.1021/acs.jpca.0c08690
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Burke, Michael P.
中科院分区：
文献类型：
--
作者：
Lei, Lei;Burke, Michael P.
由两个分子A + B缔合形成的旋转振动激发的短暂复合物AB** 通常被认为仅与惰性浴气M发生碰撞，该碰撞传递能量诱导的三分子缔合反应A + B（+M）→ AB（+M）。最近的研究表明，AB** 与第三个分子C的反应性碰撞--诱导化学三分子反应A + B + C →产物--在燃烧和行星大气中也是重要的。以前的研究与反应碰撞系统主要集中在有限范围内的反应碰撞摩尔分数，XC，和压力，P，特定于所选的应用程序。然而，它仍然有待建立如何这样的系统，以及它们的新兴的现象学反应的速率常数，表现在wideXCandPranges的潜在利益，在目前的理解，阻碍了广泛适用的速率定律和一般治疗的发展，这样的系统动力学建模的差距。在这里，我们提出的结果从主方程计算HO 2 ** 形成的H + O2及其与H的反应，以促进理解和探索系统的表示与反应对撞机在宽范围的XCandP。关于理解，我们证明了反应性碰撞可以（1）增加反应物转化为产物的总速率和（2）改变最终产物之间的分支比。关于动力学模型中的表示，我们发现所有涌现的唯象反应--三分子缔合A + B（+M）、化学三分子缔合A + B + C和双分子AB + C--的速率常数都表现出丰富的XCandP依赖性。我们还提出了分析，以探索存在一个独特的现象学表示（或缺乏），并评估反应碰撞的不同影响的动力学模型中表示的方式。
Rovibrationally excited ephemeral complexes AB**, formed from the association of two molecules A + B, are generally considered to undergo collisions only with an inert bath gas M that transfer energy—inducing termolecular association reactions A + B (+M) → AB (+M). Recent studies have demonstrated that reactive collisions of AB**with a third molecule C—inducing chemically termolecular reactions A + B + C → products—can also be significant in combustion and planetary atmospheres. Previous studies on systems with reactive collisions have primarily focused on limited ranges of reactive collider mole fraction,XC, and pressure,P, specific to the chosen application. Yet, it remains to be established how such systems, and the rate constants of their emergent phenomenological reactions, behave over the wideXCandPranges of potential interest—a gap in the present understanding that has impeded the development of broadly applicable rate laws and general treatment of such systems in kinetic modeling. Here, we present results from master equation calculations for HO2**formed from H + O2and its reactions with H to advance understanding and explore representations of systems with reactive colliders across wide ranges ofXCandP. With regard to understanding, we demonstrate that reactive collisions can both (1) increase the overall rate of conversion of reactants to products and (2) alter the branching ratio among final products. With regard to representations in kinetic models, we find that rate constants of all emergent phenomenological reactions—termolecular association A + B (+M), chemically termolecular A + B + C, and bimolecular AB + C—exhibit a richXCandPdependence. We also present analyses to explore the existence of a unique phenomenological representation (or lack thereof) and assess ways for the distinct effects of reactive collisions to be represented in kinetic models.