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

Siddharth Iyer; Avinash Kumar; Anni Savolainen; Shawon Barua; Christopher Daub; Lukas Pichelstorfer; Pontus Roldin; Olga Garmash; Prasenjit Seal; Theo Kurtén; Matti Rissanen

doi:10.1038/s41467-023-40675-2

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

Siddharth Iyer, Avinash Kumar, Anni Savolainen, Shawon Barua, Christopher Daub, Lukas Pichelstorfer, Pontus Roldin, Olga Garmash, Prasenjit Seal, Theo Kurtén, Matti Rissanen

Research output: Contribution to journal › Article › peer-review

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 including the molecular rearrangement of BPRs may be vital for accurate chemical modeling of the atmosphere.

Original language	English
Article number	4984
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-40675-2
Publication status	Published - 2023 Dec

Subject classification (UKÄ)

Theoretical Chemistry (including Computational Chemistry)

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10.1038/s41467-023-40675-2Licence: CC BY

Cite this

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title = "Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics",

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 including the molecular rearrangement of BPRs may be vital for accurate chemical modeling of the atmosphere.",

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T1 - Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics

AU - Iyer, Siddharth

AU - Kumar, Avinash

AU - Savolainen, Anni

AU - Barua, Shawon

AU - Daub, Christopher

AU - Pichelstorfer, Lukas

AU - Roldin, Pontus

AU - Garmash, Olga

AU - Seal, Prasenjit

AU - Kurtén, Theo

AU - Rissanen, Matti

PY - 2023/12

Y1 - 2023/12

N2 - 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.

AB - 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.

U2 - 10.1038/s41467-023-40675-2

DO - 10.1038/s41467-023-40675-2

M3 - Article

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VL - 14

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 4984

ER -

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

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