Direct measurements of DOCO isomers in the kinetics of OD + CO
Abstract
Quantitative and mechanistically detailed kinetics of the reaction of hydroxyl radical (OH) with carbon monoxide (CO) have been a longstanding goal of contemporary chemical kinetics. This fundamental prototype reaction plays an important role in atmospheric and combustion chemistry, motivating studies for accurate determination of the reaction rate coefficient and its pressure and temperature dependence at thermal reaction conditions. This intricate dependence can be traced directly to details of the underlying dynamics (formation, isomerization, and dissociation) involving the reactive intermediates cis- and trans-HOCO, which can only be observed transiently. Using time-resolved frequency comb spectroscopy, comprehensive mechanistic elucidation of the kinetics of the isotopic analog deuteroxyl radical (OD) with CO has been realized. By monitoring the concentrations of reactants, intermediates, and products in real time, the branching and isomerization kinetics and absolute yields of all species in the OD + CO reaction are quantified as a function of pressure and collision partner.
Additional Information
© 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). Submitted 25 July 2017. Accepted 7 December 2017. Published 12 January 2018. We thank J. M. Bowman and H. Guo for stimulating discussions. Funding: We acknowledge the financial support from the Air Force Office of Scientific Research (FA9550-15-1-0111 P00002), Defense Advanced Research Projects Agency Spectral Combs from UV to THz, National Institute of Standards and Technology, and NSF JILA Physics Frontier Center (NSF PHY-1734006). J.F.S. and T.L.N. acknowledge the financial support from the U.S. Department of Energy, Office of Basic Energy Sciences, under award number DE-FG02-07ER15884. M.O. acknowledges the support of the NSF (grant CHE-1413712) and NASA's Upper Atmosphere Research Program. T.Q.B. is supported by the National Research Council Research Associate Fellowship, and P.B.C. is supported by the NSF Graduate Research Fellowships Program. Author contributions: T.Q.B., B.J.B., M.O., and J.Y. conceived and designed the experiments. T.Q.B., B.J.B., P.B.C., and J.Y. discussed and implemented the experimental technique. T.Q.B. and B.J.B. analyzed all the data. T.L.N. and J.F.S. provided the supporting theory. All authors contributed to technical discussions and writing of the manuscript. Competing interests: All authors declare that they have no competing interests. Data and materials availability: Data are archived on a network-attached storage drive located at JILA. All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. Additional data related to this paper may be requested from the authors.Attached Files
Published - eaao4777.full.pdf
Supplemental Material - aao4777_SM.pdf
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Additional details
- PMCID
- PMC5770171
- Eprint ID
- 84362
- Resolver ID
- CaltechAUTHORS:20180117-115128648
- FA9550-15-1-0111 P00002
- Air Force Office of Scientific Research (AFOSR)
- Defense Advanced Research Projects Agency (DARPA)
- National Institute of Standards and Technology (NIST)
- PHY-1734006
- NSF
- DE-FG02-07ER15884
- Department of Energy (DOE)
- CHE-1413712
- NSF
- NASA
- National Research Council of Canada
- NSF Graduate Research Fellowship
- Created
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2018-01-18Created from EPrint's datestamp field
- Updated
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2022-03-18Created from EPrint's last_modified field