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

被引：40

作者：

Caravan, Rebecca L. ^{[1
]}

Khan, M. Anwar H. ^{[2
]}

Zador, Judit ^{[1
]}

Sheps, Leonid ^{[1
]}

Antonov, Ivan O. ^{[1
]}

Rotavera, Brandon ^{[1
]}

Ramasesha, Krupa ^{[1
]}

Au, Kendrew ^{[1
]}

Chen, Ming-Wei ^{[1
]}

Rosch, Daniel ^{[1
]}

Osborn, David L. ^{[1
]}

Fittschen, Christa ^{[3
]}

Schoemaecker, Coralie ^{[3
]}

Duncianu, Marius ^{[4
]}

Grira, Asma ^{[4
]}

Dusanter, Sebastien ^{[4
]}

Tomas, Alexandre ^{[4
]}

Percival, Carl J. ^{[5
]}

Shallcross, Dudley E. ^{[2
]}

Taatjes, Craig A. ^{[1
]}

机构：

[1] Sandia Natl Labs, Combust Res Facil, Mailstop 9055, Livermore, CA 94551 USA

[2] Univ Bristol, Sch Chem, Cantocks Close, Bristol BS8 1TS, Avon, England

[3] Univ Lille, CNRS, PC2A Physicochim Proc Combust & Atmospher, UMR 8522, F-59000 Lille, France

[4] Univ Lille, IMT Lille Douai, Dept Sci Atmosphere & Genie Environm SAGE, F-59000 Lille, France

[5] CALTECH, Jet Prop Lab, 4800 Oak Grove Dr, Pasadena, CA 91109 USA

来源：

NATURE COMMUNICATIONS | 2018年 / 9卷

关键词：

INTERMEDIATES CRI MECHANISM; OH RADICALS; PEROXY-RADICALS; GLOBAL CHEMISTRY; TRANSPORT MODEL; CH3O2; RADICALS; CROSS-SECTIONS; RATE-CONSTANT; KINETICS; YIELDS;

D O I：

10.1038/s41467-018-06716-x

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

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 inter-system crossing between singlet and triplet surfaces - similar to 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.

引用

页数：9

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