Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products

Green, Amy M.; Barber, Victoria P.; Fang, Yi; Klippenstein, Stephen J.; Lester, Marsha I.

doi:10.1073/pnas.1715014114

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products

Journal Article · Sun Nov 05 23:00:00 EST 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1715014114· OSTI ID:1408162

Green, Amy M. ^[1]; Barber, Victoria P. ^[1]; Fang, Yi ^[1]; Klippenstein, Stephen J. ^[2]; Lester, Marsha I. ^[1]

Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323,
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439

Significance

Ozonolysis of volatile biogenic and anthropogenic alkenes is a significant source of hydroxyl radicals, a key oxidant in the troposphere. A critical step in the generation of hydroxyl radicals is a hydrogen-atom transfer reaction involving a carbonyl oxide species, known as the Criegee intermediate. In this study, experiment and statistical theory reveal that selective deuteration of a Criegee intermediate results in deuterium atom transfer and slows the release of hydroxyl- d radicals. A large kinetic isotope effect is found at energies near the classical barrier to reaction and under thermal conditions relevant to the atmosphere. This demonstrates that quantum mechanical tunneling significantly enhances the rate of production of hydroxyl radicals in alkene ozonolysis reactions under atmospheric conditions.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1408162

Alternate ID(s):: OSTI ID: 1416982

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 47 Vol. 114; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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