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Stereoselectivity in Atmospheric Autoxidation

Møller, Kristian H. and Praske, Eric and Xu, Lu and Crounse, John D. and Wennberg, Paul O. and Kjaergaard, Henrik G. (2019) Stereoselectivity in Atmospheric Autoxidation. Journal of Physical Chemistry Letters, 10 (20). pp. 6260-6266. ISSN 1948-7185. doi:10.1021/acs.jpclett.9b01972.

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We show that the diastereomers of hydroxy peroxy radicals formed from OH and O_2 addition to C2 and C3, respectively, of crotonaldehyde (CH_3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC–CIMS) measurements.

Item Type:Article
Related URLs:
URLURL TypeDescription ItemData
Møller, Kristian H.0000-0001-8070-8516
Praske, Eric0000-0001-7169-4423
Xu, Lu0000-0002-0021-9876
Crounse, John D.0000-0001-5443-729X
Wennberg, Paul O.0000-0002-6126-3854
Kjaergaard, Henrik G.0000-0002-7275-8297
Additional Information:© 2019 American Chemical Society. Received: July 8, 2019; Accepted: September 23, 2019; Published: September 23, 2019. All ωB97X-D/aug-cc-pVTZ and F12 output files, which include the ωB97X-D/aug-cc-pVTZ optimized geometries are available at The authors thank Hannah M. Allen for helpful discussions. K.H.M. acknowledges the financial support of the Danish Ministry for Higher Education and Science’s Elite Research travel grant and the Niels Bohr Foundation. We are grateful for the funding from the National Science Foundation (Grant CHE-1508526), the Alfred P. Sloan Foundation’s program Chemistry of Indoor Environments, the Independent Research Fund Denmark, and the University of Copenhagen. The authors declare no competing financial interest.
Funding AgencyGrant Number
Ministry of Higher Education and Science (Denmark)UNSPECIFIED
Niels Bohr FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Independent Research Fund DenmarkUNSPECIFIED
University of CopenhagenUNSPECIFIED
Issue or Number:20
Record Number:CaltechAUTHORS:20190924-092009258
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Official Citation:Stereoselectivity in Atmospheric Autoxidation. Kristian H. Møller, Eric Praske, Lu Xu, John D. Crounse, Paul O. Wennberg, and Henrik G. Kjaergaard. The Journal of Physical Chemistry Letters 2019 10 (20), 6260-6266 DOI: 10.1021/acs.jpclett.9b01972
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:98824
Deposited By: Tony Diaz
Deposited On:24 Sep 2019 16:29
Last Modified:16 Nov 2021 17:41

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