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

Journal Article · · Nature Communications
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  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Bristol Univ. (United Kingdom)
  3. Université Lille, CNRS, UMR (France)
  4. Université Lille (France)
  5. California Inst. of Technology (CalTech), La Canada Flintridge, CA (United States). Jet Propulsion Lab.
+ Show Author Affiliations

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.

Research Organization:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & 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, Journal Name: Nature Communications Journal Issue: 1 Vol. 9; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (7)

Water Vapor Does Not Catalyze the Reaction between Methanol and OH Radicals journal March 2019
Water Vapor Does Not Catalyze the Reaction between Methanol and OH Radicals journal April 2019
ROOOH: A missing piece of the puzzle for OH measurements in low-NO environments? text January 2019
ROOOH: a missing piece of the puzzle for OH measurements in low-NO environments? journal January 2019
Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction journal January 2019
On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America journal January 2019
Chemistry and deposition in the Model of Atmospheric composition at Global and Regional scales using Inversion Techniques for Trace gas Emissions (MAGRITTE v1.1) – Part 1: Chemical mechanism journal January 2019

Figures / Tables (6)

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY