ArticlePhysical chemistry chemical physics : PCCP2025
Rapid unimolecular reactions of acyl peroxy radicals: extending the structure-activity relationships.
Article in Physical chemistry chemical physics : PCCP, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 1 paper.
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Who cites it
1 citing paper in PubMed.
- Gas-Phase Formation of Trioxy Acid via OH-Initiated Aldehyde Oxidation under Atmospheric Conditions.The journal of physical chemistry letters · 2026Article
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5 authors.
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Abstract
Acyl peroxy radicals are especially efficient at forming organic accretion products in the troposphere, but they also have short lifetimes due to rapid unimolecular reactions. For this reason, we find it important to accurately represent the reactions of these species in structure-activity relationships estimating the unimolecular reactivity of atmospheric peroxy radicals. To address this, we performed multi-conformer transition state theory calculations to determine H-shift and ring closure reaction rates for aldehyde-substituted and unsaturated acyl peroxy radicals over a wide temperature range. Similar calculations were performed for enol-substituted peroxy radicals, which are also underrepresented in SAR models. As a results, we found that H-shifts from aldehyde groups are highly competitive, that ring closures are overwhelmingly the major atmospheric fate of unsaturated acyl peroxy radicals, and that H-shifts from
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