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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >When Rate Constants Are Not Enough
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When Rate Constants Are Not Enough

机译：当速率常数不足时

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摘要

Real-world chemical systems consisting of multiple isomers and multiple reaction channels often react significantly prior to attaining a steady state energy distribution (SED). Detailed elementary reaction models, which implicitly require SED conditions, may be invalid when non-steady-state energy distributions (NSED) exist. NSED conditions may result in reaction rates and product yields that are different from those expected for SED conditions, although this problem is to some extent reduced by using phenomenological models and rate constants. The present study defines pragmatic diagnostics useful for identifying NSED conditions in stochastic master equation simulations. A representative example is presented for each of four classes of common combustion species: RO2, radicals, aliphatic hydrocarbons, alkyl radicals, and polyaromatic radicals. An example selected from the seminal work of Tsang et al. demonstrates that stochastic simulations and eigenvalue methods for solving the master equation predict the same NSED effects. NSED effects are common under relatively moderate combustion conditions, and accurate simulations may require a master equation analysis.
机译：由多个异构体和多个反应通道组成的现实世界化学系统通常会在达到稳态能量分布（SED）之前发生显着反应。当存在非稳态能量分布（NSED）时，隐式需要SED条件的详细基本反应模型可能无效。 NSED条件可能会导致反应速率和产物收率与SED条件所预期的不同，尽管通过使用现象学模型和速率常数可以在一定程度上减少此问题。本研究定义了实用的诊断方法，可用于识别随机主方程模拟中的NSED条件。针对四种常见燃烧物质中的每一种都提供了一个代表性示例：RO2，自由基，脂族烃，烷基和多芳族自由基。从Tsang等人的开创性著作中选取一个例子。证明用于求解主方程的随机模拟和特征值方法可预测相同的NSED效果。 NSED效应在相对中等的燃烧条件下很常见，准确的仿真可能需要主方程分析。

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