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Discussion papers
https://doi.org/10.5194/acp-2018-935
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2018-935
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 06 Nov 2018

Research article | 06 Nov 2018

Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

Oligomerization Reactions of Criegee Intermediates with Hydroxyalkyl Hydroperoxides: Mechanism, Kinetics, and Structure-Reactivity Relationship

Long Chen1,2, Yu Huang1,2, Yonggang Xue1,2, Zhenxing Shen3, Junji Cao1,2, and Wenliang Wang4 Long Chen et al.
  • 1Key Lab of Aerosol Chemistry & Physics, Institute of Earth Environment, Chinese Academy of Sciences, Xi’an, Shaanxi, 710061, China
  • 2State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences, Xi’an 710061, China
  • 3Department of Environmental Sciences and Engineering, Xi'an Jiaotong University, Xi'an, 710049, China
  • 4School of Chemistry and Chemical Engineering, Key Laboratory for Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi'an, Shaanxi, 710119, China

Abstract. Although secondary organic aerosols (SOAs) are major components of PM2.5 and organic aerosol (OA) particles and therefore profoundly influencing air quality, climate forcing and human health, the mechanism of SOAs formation via Criegee chemistry is poorly understood. Herein, we perform high-level theoretical calculations to study the reactivity and kinetics of four Criegee intermediates (CIs) reactions with four hydroxyalkyl hydroperoxides (HHPs) for the first time. The calculated results show that the sequential addition of CIs to HHPs affords oligomers containing CIs as chain units. The addition of -OOH group in HHPs to the central carbon atom of CIs is identified as the most energetically favorable channel, with a barrier height strongly dependent on both, CI substituent number (one or two) and position (syn- or anti-). In particular, the introduction of a methyl group into the anti-position significantly increase the rate coefficient, dramatic decrease is observed when the methyl group is introduced into the syn-position. Based on the collected data, the atmospheric lifetime of anti-CH3CHOO in the presence of HHPs is estimated as ~5.9×103s. These findings are expected to broaden the reactivity profile and deepen our understanding of atmospheric SOAs formation processes.

Long Chen et al.
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Short summary
The present calculations show that the sequential addition of CIs to HHPs affords oligomers containing CIs as chain units. The addition of -OOH group in HHPs to the central carbon atom of CIs is identified as the most energetically favorable channel, with a barrier height strongly dependent on both, CI substituent number (one or two) and position (syn- or anti-). In particular, the introduction of a methyl group into the anti-position significantly increase the rate coefficient.
The present calculations show that the sequential addition of CIs to HHPs affords oligomers...
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