High-Pressure Rate Rules for Ether Alkylperoxy Radical Isomerization.

ABSTRACT: The first isomerization reaction of an alkylperoxy (RO₂) radical holds significant importance in low-temperature oxidation, as it governs the branching ratios of the hydroperoxyalkyl (QOOH) radicals, which influence the competition between the chain-propagation and chain-branching reactions. In this study, we systematically calculated high-pressure rate rules for the RO₂ isomerization reaction of monoethers, exploring 5-, 6-, 7-, and 8-membered ring transition states. Primary, secondary, and tertiary carbon sites, where both the abstracting peroxy group and the abstracted hydrogen are located, were considered, with particular emphasis on distinguishing between secondary carbons adjacent (alpha) and nonadjacent to the ether functional group. Using the G4//B3LYP/6-311++

SUBMITTER: Mohamed SY 

PROVIDER: S-EPMC11440582 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature