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Published October 17, 2019 | Version Supplemental Material
Journal Article Open

Stereoselectivity in Atmospheric Autoxidation

Creators

  • 1. ROR icon University of Copenhagen
  • 2. ROR icon California Institute of Technology

Abstract

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.

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 https://sid.erda.dk/public/archives/bfad8e9ca7cf171e6d225371b36c3372/published-archive.html. 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.

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Additional details

Identifiers

Eprint ID
98824
Resolver ID
CaltechAUTHORS:20190924-092009258

Related works

Describes
https://sid.erda.dk/public/archives/bfad8e9ca7cf171e6d225371b36c3372/published-archive.html (URL)

Funding

Ministry of Higher Education and Science (Denmark)
Niels Bohr Foundation
NSF
CHE-1508526
Alfred P. Sloan Foundation
Independent Research Fund Denmark
University of Copenhagen

Dates

Created
2019-09-24
Created from EPrint's datestamp field
Updated
2021-11-16
Created from EPrint's last_modified field

Caltech Custom Metadata

Caltech groups
Division of Geological and Planetary Sciences (GPS)