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 et al. · Nat Commun · 2018

basic_science · Level V

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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.