Articles | Volume 25, issue 22
https://doi.org/10.5194/acp-25-15715-2025
https://doi.org/10.5194/acp-25-15715-2025
Research article
 | 
17 Nov 2025
Research article |  | 17 Nov 2025

Formation of highly oxygenated organic molecules from α-pinene photooxidation: evidence for the importance of highly oxygenated alkoxy radicals

Sungah Kang, Jürgen Wildt, Iida Pullinen, Luc Vereecken, Cheng Wu, Andreas Wahner, Sören R. Zorn, and Thomas F. Mentel

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Cited articles

Aschmann, S. M., Atkinson, R., and Arey, J.: Products of reaction of OH radicals with α-pinene, J. Geophys. Res.-Atmos., 107, 4191, https://doi.org/10.1029/2001jd001098, 2002. 
Assaf, E., Schoemaecker, C., Vereecken, L., and Fittschen, C.: Experimental and theoretical investigation of the reaction of RO2 radicals with OH radicals: Dependence of the HO2 yield on the size of the alkyl group, Int. J. Chem. Kin., 50, 670–680, https://doi.org/10.1002/kin.21191, 2018. 
Atkinson, R.: Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method, Atmos. Environ., 41, 8468–8485, https://doi.org/10.1016/j.atmosenv.2007.07.002, 2007. 
Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003a. 
Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, https://doi.org/10.1021/cr0206420, 2003b. 
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Short summary
Highly oxygenated organic molecules by atmospheric oxidation of plant emitted monoterpenes are important components in secondary organic aerosol formation. Autoxidation of organic peroxy radicals is one important pathway of their formation. We show that isomerization of highly oxygenated alkoxy radicals leads to highly oxygenated peroxy radicals that continue the autoxidation chain. Alkoxy-peroxy steps may dominate the formation of highly oxygenated molecules at high nitrogen oxide levels.
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