Abstract
Peroxy (RO 2 ) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO 2 + OH reaction for previously unexplored "R" structures (R = CH(O)CH 2 and R = CH 3 C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R′O 2 + RO. On the singlet surface, these reactions rapidly form ROOOH and R′OOOR adducts, respectively. The former decomposes to RO + HO 2 and R(O)OH + O 2 products, while the main decomposition channel for the latter is back to the reactant radicals. Decomposition rates of R′OOOR adducts varied between 103 and 0.015 s -1 at 298 K and 1 atm. The most long-lived R′OOOR adducts likely account for some fraction of the elemental compositions detected in the atmosphere that are commonly assigned to stable covalently bound dimers.
Original language | English |
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Pages (from-to) | 2051-2057 |
Number of pages | 7 |
Journal | Journal of Physical Chemistry Letters |
Volume | 10 |
Issue number | 9 |
DOIs | |
Publication status | Published - 2 May 2019 |
Publication type | A1 Journal article-refereed |
Publication forum classification
- Publication forum level 3
ASJC Scopus subject areas
- General Materials Science
- Physical and Theoretical Chemistry