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

Caravan, Rebecca L.; Khan, M. Anwar H.; Zádor, Judit; Sheps, Leonid; Antonov, Ivan O.; Rotavera, Brandon; Ramasesha, Krupa; Au, Kendrew; Chen, Ming-Wei; Rösch, Daniel; Osborn, David L.; Fittschen, Christa; Schoemaecker, Coralie; Duncianu, Marius; Grira, Asma; Dusanter, Sebastien; Tomas, Alexandre; Percival, Carl J.; Shallcross, Dudley E.; Taatjes, Craig A.

doi:10.1038/s41467-018-06716-x

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

Journal Article · Fri Oct 19 00:00:00 EDT 2018 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-06716-x· OSTI ID:1483975

^[1];

^[2]; Zádor, Judit ^[1]; Sheps, Leonid ^[1]; Antonov, Ivan O. ^[1];

^[1]; Ramasesha, Krupa ^[1]; Au, Kendrew ^[1]; Chen, Ming-Wei ^[1]; Rösch, Daniel ^[1];

^[1];

^[3]; Schoemaecker, Coralie ^[3]; Duncianu, Marius ^[4]; Grira, Asma ^[4]; Dusanter, Sebastien ^[4]; Tomas, Alexandre ^[4]; Percival, Carl J. ^[5]; Shallcross, Dudley E. ^[2];

^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Bristol Univ. (United Kingdom)
Université Lille, CNRS, UMR (France)
Université Lille (France)
California Inst. of Technology (CalTech), La Canada Flintridge, CA (United States). Jet Propulsion Lab.

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.

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Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000; NA0003525; AC02-05CH11231

OSTI ID:: 1483975

Report Number(s):: SAND-2018-11575J; 669351

Journal Information:: Nature Communications, Vol. 9, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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