Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics
(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.
(Less)
- author
- organization
- publishing date
- 2023-12
- 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}}, }