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Title: 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Colorado, Boulder, CO (United States). JILA. National Inst. of Standards and Technology. Dept. of Physics
  2. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
  3. California Inst. of Technology (CalTech), Pasadena, CA (United States). Arthur Amos Noyes Lab. of Chemical Physics
Publication Date:
Research Org.:
Univ. of Florida, Gainesville, FL (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States); Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)
OSTI Identifier:
1499948
Grant/Contract Number:  
FG02-07ER15884; FA9550-15-1-0111 P00002; PHY-1734006; CHE-1413712
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bui, Thinh Q., Bjork, Bryce J., Changala, P. Bryan, Nguyen, Thanh L., Stanton, John F., Okumura, Mitchio, and Ye, Jun. Direct measurements of DOCO isomers in the kinetics of OD + CO. United States: N. p., 2018. Web. doi:10.1126/sciadv.aao4777.
Bui, Thinh Q., Bjork, Bryce J., Changala, P. Bryan, Nguyen, Thanh L., Stanton, John F., Okumura, Mitchio, & Ye, Jun. Direct measurements of DOCO isomers in the kinetics of OD + CO. United States. doi:10.1126/sciadv.aao4777.
Bui, Thinh Q., Bjork, Bryce J., Changala, P. Bryan, Nguyen, Thanh L., Stanton, John F., Okumura, Mitchio, and Ye, Jun. Fri . "Direct measurements of DOCO isomers in the kinetics of OD + CO". United States. doi:10.1126/sciadv.aao4777. https://www.osti.gov/servlets/purl/1499948.
@article{osti_1499948,
title = {Direct measurements of DOCO isomers in the kinetics of OD + CO},
author = {Bui, Thinh Q. and Bjork, Bryce J. and Changala, P. Bryan and Nguyen, Thanh L. and Stanton, John F. and Okumura, Mitchio and Ye, Jun},
abstractNote = {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.},
doi = {10.1126/sciadv.aao4777},
journal = {Science Advances},
issn = {2375-2548},
number = 1,
volume = 4,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 8 works
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Figures / Tables:

Fig. 1. Fig. 1.: The OH + CO reaction PES with energies in kilojoules per mole. The colored PES in the background depicts the HOCO isomer potential energy wells along the H–O–C–O dihedral angle (parallel to page) and O–H bond length (perpendicular to page).

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.