Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
17 Aug 2023
17 Aug 2023
Historique:
received:
24
03
2023
accepted:
07
08
2023
medline:
18
8
2023
pubmed:
18
8
2023
entrez:
17
8
2023
Statut:
epublish
Résumé
The oxidation of aromatics contributes significantly to the formation of atmospheric aerosol. Using toluene as an example, we demonstrate the existence of a molecular rearrangement channel in the oxidation mechanism. Based on both flow reactor experiments and quantum chemical calculations, we show that the bicyclic peroxy radicals (BPRs) formed in OH-initiated aromatic oxidation are much less stable than previously thought, and in the case of the toluene derived ipso-BPRs, lead to aerosol-forming low-volatility products with up to 9 oxygen atoms on sub-second timescales. Similar results are predicted for ipso-BPRs formed from many other aromatic compounds. This reaction class is likely a key route for atmospheric aerosol formation, and including the molecular rearrangement of BPRs may be vital for accurate chemical modeling of the atmosphere.
Identifiants
pubmed: 37591852
doi: 10.1038/s41467-023-40675-2
pii: 10.1038/s41467-023-40675-2
pmc: PMC10435581
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
4984Subventions
Organisme : Vetenskapsrådet (Swedish Research Council)
ID : 2019-05006
Organisme : Svenska Forskningsrådet Formas (Swedish Research Council Formas)
ID : 2018-01745
Organisme : EC | Horizon 2020 Framework Programme (EU Framework Programme for Research and Innovation H2020)
ID : 101002728
Organisme : Academy of Finland (Suomen Akatemia)
ID : 331207
Organisme : Academy of Finland (Suomen Akatemia)
ID : 336531
Commentaires et corrections
Type : ErratumIn
Informations de copyright
© 2023. Springer Nature Limited.
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