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Updated: Oct 19, 2025

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Mechanism and kinetics for the reaction of methyl peroxy radical with O2
Sandhiya Lakshmanan1,2, William L Hase1, Gregory P Smith3
1Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409, USA. sandhiya@nistads.res.in.
Abstract:
Quantum chemical calculations and dynamics simulations were performed to study the reaction between methyl peroxy radical (CH3O2) and O2. The reaction proceeds through three different pathways (1) H-atom abstraction, (2) O2 addition and (3) concerted H-atom shift and O2 addition reactions. The concerted H-atom shift and O2 addition pathway is the most favourable reaction both kinetically and thermodynamically. The major product channel formed from these reactions is H2CO + OH + O2. Trajectory calculations also confirm that H2CO + OH + O2 is the main product channel. An estimated rate constant expression for this reaction from master equation calculations is 4.20 × 1013 e-8676/T cm3 mole-1 s-1.
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