Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction
Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction
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DOI：
10.5194/acp-19-7691-2019
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发表时间：
2019-06-07
影响因子：
6.3
通讯作者：
Rickard, Andrew R.
中科院分区：
文献类型：
--
作者：
Jenkin, Michael E.;Valorso, Richard;Rickard, Andrew R.
有机过氧自由基（RO 2）是由碳氢化合物和其他挥发性有机化合物（VOCs）降解形成的，在对流层氧化机制中起着关键作用。对于给定的RO（2）自由基，可能存在几种竞争反应，其相对速率取决于RO 2的结构和环境条件。发表的动力学和分支比的数据进行审查的双分子反应的RO 2与NO，NO2，NO3，OH和HO 2的;和他们的自我反应和交叉反应与其他RO 2自由基。该信息用于定义通用速率系数和结构-活性关系（SAR）方法，该方法可应用于一系列重要类别的烃和含氧RO 2自由基的双分子反应。选定的单分子异构化反应（即氢原子移位和闭环反应）的信息也进行了总结和讨论。这里提出的方法旨在指导下一代明确详细的化学机制中RO 2自由基化学的表示。
Organic peroxy radicals (RO2), formed from the degradation of hydrocarbons and other volatile organic compounds (VOCs), play a key role in tropospheric oxidation mechanisms. Several competing reactions may be available for a given RO(2 )radical, the relative rates of which depend on both the structure of RO2 and the ambient conditions. Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3, OH and HO2; and for their self-reactions and cross-reactions with other RO2 radicals. This information is used to define generic rate coefficients and structure-activity relationship (SAR) methods that can be applied to the bimolecular reactions of a series of important classes of hydrocarbon and oxygenated RO2 radicals. Information for selected unimolecular isomerization reactions (i.e. H-atom shift and ring-closure reactions) is also summarized and discussed. The methods presented here are intended to guide the representation of RO2 radical chemistry in the next generation of explicit detailed chemical mechanisms.