Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

Michael E. Jenkin*, Richard Valorso, Bernard Aumont, Andrew R. Rickard

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

17 Citations (Scopus)
144 Downloads (Pure)

Abstract

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 RO2 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.

Original languageEnglish
Pages (from-to)7691-7717
Number of pages27
JournalAtmospheric Chemistry and Physics
Volume19
Issue number11
DOIs
Publication statusPublished - 7 Jun 2019

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