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The reaction of hydroxyl and methylperoxy radicals is not a major source of atmospheric methanol

Author

Listed:
  • Rebecca L. Caravan

    (Mailstop 9055, Sandia National Laboratories)

  • M. Anwar H. Khan

    (School of Chemistry, Cantock’s Close, University of Bristol)

  • Judit Zádor

    (Mailstop 9055, Sandia National Laboratories)

  • Leonid Sheps

    (Mailstop 9055, Sandia National Laboratories)

  • Ivan O. Antonov

    (Mailstop 9055, Sandia National Laboratories)

  • Brandon Rotavera

    (Mailstop 9055, Sandia National Laboratories)

  • Krupa Ramasesha

    (Mailstop 9055, Sandia National Laboratories)

  • Kendrew Au

    (Mailstop 9055, Sandia National Laboratories)

  • Ming-Wei Chen

    (Mailstop 9055, Sandia National Laboratories)

  • Daniel Rösch

    (Mailstop 9055, Sandia National Laboratories)

  • David L. Osborn

    (Mailstop 9055, Sandia National Laboratories)

  • Christa Fittschen

    (Université Lille, CNRS, UMR 8522–PC2A–Physicochimie des Processus de Combustion et de l’Atmosphère)

  • Coralie Schoemaecker

    (Université Lille, CNRS, UMR 8522–PC2A–Physicochimie des Processus de Combustion et de l’Atmosphère)

  • Marius Duncianu

    (IMT Lille Douai, Université Lille, Département Sciences de l’Atmosphère et Génie de l’Environnement (SAGE))

  • Asma Grira

    (IMT Lille Douai, Université Lille, Département Sciences de l’Atmosphère et Génie de l’Environnement (SAGE))

  • Sebastien Dusanter

    (IMT Lille Douai, Université Lille, Département Sciences de l’Atmosphère et Génie de l’Environnement (SAGE))

  • Alexandre Tomas

    (IMT Lille Douai, Université Lille, Département Sciences de l’Atmosphère et Génie de l’Environnement (SAGE))

  • Carl J. Percival

    (California Institute of Technology)

  • Dudley E. Shallcross

    (School of Chemistry, Cantock’s Close, University of Bristol)

  • Craig A. Taatjes

    (Mailstop 9055, Sandia National Laboratories)

Abstract

Methanol is a benchmark for understanding tropospheric oxidation, but is underpredicted by up to 100% in atmospheric models. Recent work has suggested this discrepancy can be reconciled by the rapid reaction of hydroxyl and methylperoxy radicals with a methanol branching fraction of 30%. However, for fractions below 15%, methanol underprediction is exacerbated. Theoretical investigations of this reaction are challenging because of intersystem crossing between singlet and triplet surfaces – ∼45% of reaction products are obtained via intersystem crossing of a pre-product complex – which demands experimental determinations of product branching. Here we report direct measurements of methanol from this reaction. A branching fraction below 15% is established, consequently highlighting a large gap in the understanding of global methanol sources. These results support the recent high-level theoretical work and substantially reduce its uncertainties.

Suggested Citation

  • Rebecca L. Caravan & M. Anwar H. Khan & Judit Zádor & Leonid Sheps & Ivan O. Antonov & Brandon Rotavera & Krupa Ramasesha & Kendrew Au & Ming-Wei Chen & Daniel Rösch & David L. Osborn & Christa Fittsc, 2018. "The reaction of hydroxyl and methylperoxy radicals is not a major source of atmospheric methanol," Nature Communications, Nature, vol. 9(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-018-06716-x
    DOI: 10.1038/s41467-018-06716-x
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