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Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics

Iyer, Siddharth ; Kumar, Avinash ; Savolainen, Anni ; Barua, Shawon ; Daub, Christopher ; Pichelstorfer, Lukas ; Roldin, Pontus LU ; Garmash, Olga ; Seal, Prasenjit and Kurtén, Theo , et al. (2023) In Nature Communications 14(1).
Abstract

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... (More)

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.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Nature Communications
volume
14
issue
1
article number
4984
publisher
Nature Publishing Group
external identifiers
  • pmid:37591852
  • scopus:85168277059
ISSN
2041-1723
DOI
10.1038/s41467-023-40675-2
language
English
LU publication?
yes
id
483ff089-7a23-4030-9da9-6434774576bd
date added to LUP
2023-09-18 10:24:37
date last changed
2024-04-19 01:10:24
@article{483ff089-7a23-4030-9da9-6434774576bd,
  abstract     = {{<p>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.</p>}},
  author       = {{Iyer, Siddharth and Kumar, Avinash and Savolainen, Anni and Barua, Shawon and Daub, Christopher and Pichelstorfer, Lukas and Roldin, Pontus and Garmash, Olga and Seal, Prasenjit and Kurtén, Theo and Rissanen, Matti}},
  issn         = {{2041-1723}},
  language     = {{eng}},
  number       = {{1}},
  publisher    = {{Nature Publishing Group}},
  series       = {{Nature Communications}},
  title        = {{Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics}},
  url          = {{http://dx.doi.org/10.1038/s41467-023-40675-2}},
  doi          = {{10.1038/s41467-023-40675-2}},
  volume       = {{14}},
  year         = {{2023}},
}