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

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 Fittschen, Coralie Schoemaecker, Marius Duncianu, Asma Grira, Sebastien Dusanter, Alexandre Tomas, Carl J. Percival, Dudley E. Shallcross () and Craig A. Taatjes ()
Additional contact information
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

Nature Communications, 2018, vol. 9, issue 1, 1-9

Abstract: 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.

Date: 2018
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DOI: 10.1038/s41467-018-06716-x

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