title: Direct frequency comb measurement of OD + CO → DOCO kinetics.
abstract: The kinetics of the hydroxyl radical (OH) + carbon monoxide (CO) reaction, which is fundamental to both atmospheric and combustion chemistry, are complex because of the formation of the hydrocarboxyl radical (HOCO) intermediate. Despite extensive studies of this reaction, HOCO has not been observed under thermal reaction conditions. Exploiting the sensitive, broadband, and high-resolution capabilities of time-resolved cavity-enhanced direct frequency comb spectroscopy, we observed deuteroxyl radical (OD) + CO reaction kinetics and detected stabilized trans-DOCO, the deuterated analog of trans-HOCO. By simultaneously measuring the time-dependent concentrations of the trans-DOCO and OD species, we observed unambiguous low-pressure termolecular dependence of the reaction rate coefficients for N2and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield.
authors: JILA, National Institute of Standards and Technology and University of Colorado, and Department of Physics, University of Colorado, Boulder, CO 80309, USA. bryce.bjork@colorado.edu ye@jila.colorado.edu.
authors: B J
authors: BJ
authors: Bjork
authors: JILA, National Institute of Standards and Technology and University of Colorado, and Department of Physics, University of Colorado, Boulder, CO 80309, USA.
authors: T Q
authors: TQ
authors: Bui
authors: JILA, National Institute of Standards and Technology and University of Colorado, and Department of Physics, University of Colorado, Boulder, CO 80309, USA.
authors: O H
authors: OH
authors: Heckl
authors: JILA, National Institute of Standards and Technology and University of Colorado, and Department of Physics, University of Colorado, Boulder, CO 80309, USA.
authors: P B
authors: PB
authors: Changala
authors: JILA, National Institute of Standards and Technology and University of Colorado, and Department of Physics, University of Colorado, Boulder, CO 80309, USA.
authors: B
authors: B
authors: Spaun
authors: Crystalline Mirror Solutions, 114 East Haley Street, Suite G, Santa Barbara, CA 93101, USA.
authors: P
authors: P
authors: Heu
authors: Crystalline Mirror Solutions, 114 East Haley Street, Suite G, Santa Barbara, CA 93101, USA.
authors: D
authors: D
authors: Follman
authors: Crystalline Mirror Solutions, Parkring 10, 1010 Vienna, Austria.
authors: C
authors: C
authors: Deutsch
authors: Crystalline Mirror Solutions, 114 East Haley Street, Suite G, Santa Barbara, CA 93101, USA. Crystalline Mirror Solutions, Parkring 10, 1010 Vienna, Austria.
authors: G D
authors: GD
authors: Cole
authors: Vienna Center for Quantum Science and Technology, Faculty of Physics, University of Vienna, 1090 Vienna, Austria.
authors: M
authors: M
authors: Aspelmeyer
authors: Arthur Amos Noyes Laboratory of Chemical Physics, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Pasadena, CA 91125, USA.
authors: M
authors: M
authors: Okumura
authors: JILA, National Institute of Standards and Technology and University of Colorado, and Department of Physics, University of Colorado, Boulder, CO 80309, USA. bryce.bjork@colorado.edu ye@jila.colorado.edu.
authors: J
authors: J
authors: Ye