In this series of two papers, we present a novel physically sound kinetic submechanism aimed at modeling the formation and decay of chemiluminescent (electronically excited) OH molecules in the ignition and combustion of hydrogen and hydrogen-based mixtures over a wide range of thermodynamic parameters and mixture compositions. The present part of this series describes the preparatory stages of the work, such as the aggregation of the data set for the OH chemiluminescent emission (including the OH emission profiles obtained in our shock-tube experiments), the choice of the basic kinetic model of hydrogen oxidation, and, importantly, quantum chemical calculations and theoretical estimates for the rate constant of the nonadiabatic preassociation reaction H + O + M OH + M, recognized as a major source of excited OH molecules in hydrogen-air flames. These rate constant estimates are carried out in a wide range of temperatures (200–4000 K) and pressures ( bar). It is shown that the rate constant of this key reaction exhibits distinct non-Arrhenius temperature behavior and, moreover, has a complex fall-off pressure dependence, with the transition from a third to a second-order, high-pressure regime occurring at pressures about 10 atm. The obtained dependence on temperature and pressure is in excellent agreement with the known experimental data and can be recommended (as part of the appropriate reaction mechanisms) for further kinetic modeling of OH chemiluminescence accompanying the high-temperature oxidation of hydrogen and other fuels.

中文翻译：

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重新审视氢燃烧中 OH[省略式]化学发光的详细动力学子机制。第1部分

在这一系列的两篇论文中，我们提出了一种新颖的物理合理的动力学子机制，旨在模拟氢和氢基混合物在各种热力学参数的点火和燃烧过程中化学发光（电子激发）OH分子的形成和衰变，以及混合物组合物。本系列的当前部分描述了工作的准备阶段，例如 OH 化学发光发射数据集的聚合（包括在我们的激波管实验中获得的 OH 发射曲线）、基本动力学模型的选择氢气氧化，以及重要的是非绝热预缔合反应 H + O + M OH + M 的量子化学计算和速率常数的理论估计，该反应被认为是氢-空气火焰中激发的 OH 分子的主要来源。这些速率常数估计是在较宽的温度 (200–4000 K) 和压力 (bar) 范围内进行的。结果表明，这一关键反应的速率常数表现出明显的非阿累尼乌斯温度行为，而且具有复杂的下降压力依赖性，在压力下发生从三阶高压状态到二阶高压状态的转变。约10个大气压。所获得的对温度和压力的依赖性与已知的实验数据非常一致，并且可以推荐（作为适当反应机制的一部分）用于伴随氢气和其他燃料的高温氧化的OH化学发光的进一步动力学建模。