title: Hydroxyacetone Production From C3Criegee Intermediates.
abstract: Hydroxyacetone (CH3C(O)CH2OH) is observed as a stable end product from reactions of the (CH3)2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerization via hydrogen atom transfer and -OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. The hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , Livermore, California 94551-0969, United States.
authors.forename: Craig A
authors.initials: CA
authors.lastname: Taatjes
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Fang
authors.initials: F
authors.lastname: Liu
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , Livermore, California 94551-0969, United States.
authors.forename: Brandon
authors.initials: B
authors.lastname: Rotavera
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588-0304, United States.
authors.forename: Manoj
authors.initials: M
authors.lastname: Kumar
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , Livermore, California 94551-0969, United States.
authors.forename: Rebecca
authors.initials: R
authors.lastname: Caravan
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , Livermore, California 94551-0969, United States.
authors.forename: David L
authors.initials: DL
authors.lastname: Osborn
authors.affiliation: Department of Chemistry, University of Kansas , Lawrence, Kansas 66045, United States.
authors.forename: Ward H
authors.initials: WH
authors.lastname: Thompson
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Marsha I
authors.identifier: http://orcid.org/0000-0003-2367-3497
authors.initials: MI
authors.lastname: Lester