Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts

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Iyer , S , Rissanen , M P & Kurtén , T 2019 , ' Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts ' , Journal of Physical Chemistry Letters , vol. 10 , no. 9 , pp. 2051-2057 . https://doi.org/10.1021/acs.jpclett.9b00405

Title: Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts
Author: Iyer, Siddharth; Rissanen, Matti P.; Kurtén, Theo
Contributor: University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
University of Helsinki, INAR Physics
University of Helsinki, Department of Chemistry
Date: 2019-05-02
Language: eng
Number of pages: 13
Belongs to series: Journal of Physical Chemistry Letters
ISSN: 1948-7185
URI: http://hdl.handle.net/10138/301871
Abstract: Peroxy (RO2) 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 RO2 + OH reaction for previously unexplored “R” structures (R = CH(O)CH2 and R = CH3C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R′O2 + RO. On the singlet surface, these reactions rapidly form ROOOH and R′OOOR adducts, respectively. The former decomposes to RO + HO2 and R(O)OH + O2 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.
Subject: 116 Chemical sciences
MOLECULAR-ORBITAL METHODS
GAS-PHASE OZONOLYSIS
OH RADICALS
BASIS-SETS
CONFORMATIONAL ENERGIES
ORGANIC-COMPOUNDS
CH3O2 RADICALS
RO2 RADICALS
FIELD
PRODUCTS
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