TY - JOUR
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
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 - 2023/12
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 - Journal article
C2 - 37591852
AN - SCOPUS:85168277059
SN - 2041-1723
VL - 14
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 4984
ER -