Decomposition pathways of isoprene-derived hydrotrioxides and their clustering abilities in the atmosphere

Abstract

In atmospheric gas-phase chemistry, hydrotrioxides (ROOOH) are formed as intermediates in the reactions of peroxyl radicals (RO2) with OH radicals, and their stabilization has been confirmed experimentally by direct observation. In this study, we systematically investigated the probable decomposition pathways of isoprene-derived ROOOHs in the atmosphere. The kinetic analysis confirmed that the fast fragmentation of hydrotrioxides into their respective alkoxy radicals and hydroperoxyl radicals dominates over the other decomposition mechanisms. We also explored the decomposition of ROOOH proceeding via 3(RO ··· HO2) product complexes, through which an intermolecular hydrogen transfer results in the formation of alcohol and molecular oxygen with a relatively low energy barrier. Furthermore, we studied the clustering abilities of hydrotrioxides with various types of atmospheric vapors, particularly acids and amines. The results indicate that the binding strength of these hydrotrioxides with other vapors is too low to drive clustering process at ambient atmospheric concentrations, however, hydrotrioxides interact more strongly with bases and acid–base clusters than alcohols or hydroperoxides. These findings provide insight into the atmospheric stability and reactivity of hydrotrioxides, with implications for understanding their role in processes such as secondary organic aerosol formation.

Supplementary files

Article information

Article type
Paper
Submitted
13 Nov 2024
Accepted
21 Feb 2025
First published
21 Feb 2025
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024, Accepted Manuscript

Decomposition pathways of isoprene-derived hydrotrioxides and their clustering abilities in the atmosphere

E. Ahongshangbam, L. Franzon, T. Golin Almeida, G. Hasan, B. Frandsen and N. Myllys, Phys. Chem. Chem. Phys., 2024, Accepted Manuscript , DOI: 10.1039/D4CP04329D

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