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Direct frequency comb measurement of OD + CO → DOCO kinetics

Bjork, B. J. and Bui, T. Q. and Heckl, O. H. and Changala, P. B. and Spaun, B. and Heu, P. and Follman, D. and Deutsch, C. and Cole, G. D. and Aspelmeyer, M. and Okumura, M. and Ye, J. (2016) Direct frequency comb measurement of OD + CO → DOCO kinetics. Science, 354 (6311). pp. 444-448. ISSN 0036-8075. http://resolver.caltech.edu/CaltechAUTHORS:20161107-094113128

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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 N_2 and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.aag1862DOIArticle
http://science.sciencemag.org/content/354/6311/444PublisherArticle
http://www.sciencemag.org/content/354/6311/444/suppl/DC1PublisherSupplementary Materials
ORCID:
AuthorORCID
Bui, T. Q.0000-0001-6090-0930
Okumura, M.0000-0001-6874-1137
Additional Information:© 2016 American Association for the Advancement of Science. Received 20 May 2016; resubmitted 24 August 2016. Accepted 28 September 2016. Additional data supporting the conclusions are available in supplementary materials. We thank K. Sung of the NASA Jet Propulsion Laboratory (JPL) for providing a list of D2O mid-IR line positions and intensities measured by R. A. Toth of JPL. We acknowledge financial support from the Air Force Office of Scientific Research, the Defense Advanced Research Projects Agency (DARPA) Spectral Combs from UV to THz (SCOUT) program, the National Institute of Standards and Technology, NSF, and DARPA (grants FAA-9550-14-C-0030 and W31P4Q-16-C-0001). M.O. is supported by NSF grant CHE-1413712. T.Q.B. and B.S. are supported by the National Research Council Research Associate Fellowship, P.B.C. is supported by the NSF Graduate Research Fellowship Program, and O.H.H. is partially supported through a Humboldt Fellowship. P.H., D.F., and C.D. are employees of a startup company (Crystalline Mirror Solutions), cofounded by G.D.C. and M.A., and coinventors on a submitted patent focusing on the crystalline mirror technology applied in this Report.
Funders:
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
National Institute of Standards and Technology (NIST)UNSPECIFIED
Defense Advanced Research Projects Agency (DARPA)FAA-9550-14-C-0030
Defense Advanced Research Projects Agency (DARPA)W31P4Q-16-C-0001
NSFCHE-1413712
National Research CouncilUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Alexander von Humboldt FoundationUNSPECIFIED
Record Number:CaltechAUTHORS:20161107-094113128
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20161107-094113128
Official Citation:Direct frequency comb measurement of OD + CO → DOCO kinetics By B. J. Bjork, T. Q. Bui, O. H. Heckl, P. B. Changala, B. Spaun, P. Heu, D. Follman, C. Deutsch, G. D. Cole, M. Aspelmeyer, M. Okumura, J. Ye Science 28 Oct 2016: Vol. 354, Issue 6311, pp. 444-448 DOI: 10.1126/science.aag1862
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:71766
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Nov 2016 19:10
Last Modified:19 Oct 2018 18:22

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