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

Physics

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

7 Citations (Scopus)

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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
Publication type	A1 Journal article-refereed

Funding

We thank the TofTools team for the data analysis tools and the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. We also thank Nino Runeberg of CSC for help with wavefunction stability checks. This project has received funding from the European Reasearch Council under the European Union’s Horizon 2020 research and innovation program under Grant No. 101002728 (M.R.). The support from the Academy of Finland 331207, 336531, 346373 (M.R.), the Swedish Research Council VR 2019-05006 (P.R.) and the Swedish Research Council FORMAS 2018-01745 (P.R.) are also acknowledged. We thank the TofTools team for the data analysis tools and the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. We also thank Nino Runeberg of CSC for help with wavefunction stability checks. This project has received funding from the European Reasearch Council under the European Union’s Horizon 2020 research and innovation program under Grant No. 101002728 (M.R.). The support from the Academy of Finland 331207, 336531, 346373 (M.R.), the Swedish Research Council VR 2019-05006 (P.R.) and the Swedish Research Council FORMAS 2018-01745 (P.R.) are also acknowledged.

Publication forum classification

Publication forum level 3

ASJC Scopus subject areas

General Chemistry
General Biochemistry,Genetics and Molecular Biology
General Physics and Astronomy

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

s41467-023-40675-2Final published version, 964 KBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202309128120Licence: 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.",

author = "Siddharth Iyer and Avinash Kumar and Anni Savolainen and Shawon Barua and Christopher Daub and Lukas Pichelstorfer and Pontus Roldin and Olga Garmash and Prasenjit Seal and Theo Kurt{\'e}n and Matti Rissanen",

note = "Funding Information: We thank the TofTools team for the data analysis tools and the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. We also thank Nino Runeberg of CSC for help with wavefunction stability checks. This project has received funding from the European Reasearch Council under the European Union{\textquoteright}s Horizon 2020 research and innovation program under Grant No. 101002728 (M.R.). The support from the Academy of Finland 331207, 336531, 346373 (M.R.), the Swedish Research Council VR 2019-05006 (P.R.) and the Swedish Research Council FORMAS 2018-01745 (P.R.) are also acknowledged. Funding Information: We thank the TofTools team for the data analysis tools and the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. We also thank Nino Runeberg of CSC for help with wavefunction stability checks. This project has received funding from the European Reasearch Council under the European Union{\textquoteright}s Horizon 2020 research and innovation program under Grant No. 101002728 (M.R.). The support from the Academy of Finland 331207, 336531, 346373 (M.R.), the Swedish Research Council VR 2019-05006 (P.R.) and the Swedish Research Council FORMAS 2018-01745 (P.R.) are also acknowledged. Publisher Copyright: {\textcopyright} 2023, Springer Nature Limited.",

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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

N1 - Funding Information: We thank the TofTools team for the data analysis tools and the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. We also thank Nino Runeberg of CSC for help with wavefunction stability checks. This project has received funding from the European Reasearch Council under the European Union’s Horizon 2020 research and innovation program under Grant No. 101002728 (M.R.). The support from the Academy of Finland 331207, 336531, 346373 (M.R.), the Swedish Research Council VR 2019-05006 (P.R.) and the Swedish Research Council FORMAS 2018-01745 (P.R.) are also acknowledged. Funding Information: We thank the TofTools team for the data analysis tools and the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. We also thank Nino Runeberg of CSC for help with wavefunction stability checks. This project has received funding from the European Reasearch Council under the European Union’s Horizon 2020 research and innovation program under Grant No. 101002728 (M.R.). The support from the Academy of Finland 331207, 336531, 346373 (M.R.), the Swedish Research Council VR 2019-05006 (P.R.) and the Swedish Research Council FORMAS 2018-01745 (P.R.) are also acknowledged. Publisher Copyright: © 2023, Springer Nature Limited.

PY - 2023

Y1 - 2023

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.

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DO - 10.1038/s41467-023-40675-2

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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

Abstract

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