Direct measurements of DOCO isomers in the kinetics of OD + CO

Bui, Thinh Q.; Bjork, Bryce J.; Changala, P. Bryan; Nguyen, Thanh L.; Stanton, John F.; Okumura, Mitchio; Ye, Jun

doi:10.1126/sciadv.aao4777

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:

^[1];

^[2]; Stanton, John F. ^[2];

^[3];

^[1]

Univ. of Colorado, Boulder, CO (United States). JILA. National Inst. of Standards and Technology. Dept. of Physics
Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
California Inst. of Technology (CalTech), Pasadena, CA (United States). Arthur Amos Noyes Lab. of Chemical Physics

Publication Date:: Fri Jan 12 00:00:00 EST 2018

Research Org.:: Univ. of Florida, Gainesville, FL (United States); California Institute 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); 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:: 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.

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                    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.  https://doi.org/10.1126/sciadv.aao4777

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                    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.  https://doi.org/10.1126/sciadv.aao4777.  https://www.osti.gov/servlets/purl/1499948.

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@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},

  number       = 1,

  volume       = 4,

  place        = {United States},

  year         = {Fri Jan 12 00:00:00 EST 2018},

  month        = {Fri Jan 12 00:00:00 EST 2018}

}

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https://doi.org/10.1126/sciadv.aao4777

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Cited by: 16 works

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Figures / Tables:

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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Works referenced in this record:

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Fast molecular fingerprinting with a coherent, rapidly tunable dual-comb spectrometer near 3 μm
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High-resolution infrared spectroscopy of jet cooled trans -deuteroxycarbonyl ( trans -DOCO) radical
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Kortyna, A.; Nesbitt, D. J.
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Spectral analyses of trans - and cis -DOCO transients via comb spectroscopy
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Iwakuni, Kana; Porat, Gil; Bui, Thinh Q.
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Time-resolved mid-infrared dual-comb spectroscopy
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Abbas, Muhammad A.; Pan, Qing; Mandon, Julien
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DOI: 10.1038/s41598-019-53825-8

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Title: Direct measurements of DOCO isomers in the kinetics of OD + CO

Abstract

Citation Formats

Figures / Tables:

Mid-Infrared Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals journal, June 2014

Pure rotational spectra of the CO– trans -HOCO complex journal, October 2012

Kinetics of the OH + CO reaction under atmospheric conditions journal, January 1986

Kinetics of the reaction OH + CO under atmospheric conditions journal, August 2001

Infrared Spectrum and Structure of Intermediates in the Reaction of OH with CO journal, February 1971

Forward and reverse rate coefficients in equilibrating isomerization reactions journal, April 1992

Reaction of HO with CO: Tunneling Is Indeed Important journal, May 2012

Isotopic studies of trans- and cis- HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures journal, March 2016

Reaction between hydroxyl (deuteroxyl) radicals and carbon monoxide at temperatures down to 80 K: experiment and theory journal, November 1993

HOCO Radical Chemistry journal, December 2010

Semiclassical transition state theory. A new perspective journal, October 1993

Quantum dynamics of complex-forming bimolecular reactions journal, January 2012

Modeling the Kinetics of Bimolecular Reactions journal, November 2006

Energy and structure of the transition states in the reaction OH + CO ? H + CO2 journal, January 1991

High pressure range of the addition of HO to HO, NO, NO 2 , and CO. I. Saturated laser induced fluorescence measurements at 298 K journal, August 1995

High pressure range of addition reactions of HO. II. Temperature and pressure dependence of the reaction HO+CO⇔HOCO→H+CO 2 journal, July 1996

Direct frequency comb measurement of OD + CO -> DOCO kinetics journal, October 2016

Semi-classical theory for non-separable systems:. Construction of “good” action-angle variables for reaction rate constants journal, January 1977

OD + CO → D + CO 2 branching kinetics probed with time-resolved frequency comb spectroscopy journal, September 2017

Photolysis of the OC⋯HONO complex in low temperature matrices: Infrared detection and ab initio calculations of nitrosoformic acid, HOC(O)NO journal, January 2003

Kinetics of OH(v= 0, 1) and OD(v= 0, 1) with CO and the mechanism of the OH + CO reaction journal, January 1988

Molecular collisions, from warm to ultracold journal, January 2009

Master Equation Analysis of Pressure-Dependent Atmospheric Reactions journal, December 2003

Kinetic study of the reaction of OH with CO from 250 to 1040 K journal, August 1983

Broadband Cavity Ringdown Spectroscopy for Sensitive and Rapid Molecular Detection journal, March 2006

Pressure and temperature dependence of reactions proceeding via a bound complex. An approach for combustion and atmospheric chemistry modelers. Application to HO + CO ? [HOCO] ? H + CO2 journal, January 1988

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide journal, October 2010

Observation of the pure rotational spectra of trans - and cis -HOCO journal, May 2011

The HITRAN2012 molecular spectroscopic database journal, November 2013

Molecular Transitions and Chemical Reaction Rates: The stochastic model relates the rate of a chemical reaction to the underlying transition probabilities journal, June 1965

HO + CO Reaction Rates and H/D Kinetic Isotope Effects: Master Equation Models with ab Initio SCTST Rate Constants journal, January 2013

Cold molecules: Progress in quantum engineering of chemistry and quantum matter journal, September 2017

The pressure dependence of the rate constant of the reaction of OH radicals with CO journal, January 1984

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics journal, July 2004

The pressure dependence of the rate constant of the reaction of OD radicals with CO journal, November 1982

PGOPHER: A program for simulating rotational, vibrational and electronic spectra journal, January 2017

OH(OD) + CO: Measurements and an Optimized RRKM Fit journal, October 1998

Modeling the Kinetics of Bimolecular Reactions journal, January 2007

Cold molecules: Progress in Quantum Engineering of Chemistry and Quantum Matter text, January 2017

Modeling the Kinetics of Bimolecular Reactions journal, January 2007

HOCO Radical Chemistry journal, December 2010

Master Equation Analysis of Pressure-Dependent Atmospheric Reactions journal, December 2003

Molecular collisions, from warm to ultracold journal, January 2009

Spectroscopy and dynamics of the HOCO radical: insights into the OH + CO → H + CO 2 reaction journal, January 2014

Observation of the pure rotational spectra of trans - and cis -HOCO journal, May 2011

Pure rotational spectra of the CO– trans -HOCO complex journal, October 2012

Isotopic studies of trans- and cis- HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures journal, March 2016

Broadband Cavity Ringdown Spectroscopy for Sensitive and Rapid Molecular Detection journal, March 2006

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide journal, October 2010

Molecular Transitions and Chemical Reaction Rates: The stochastic model relates the rate of a chemical reaction to the underlying transition probabilities journal, June 1965

Direct frequency comb measurement of OD + CO -> DOCO kinetics journal, October 2016

Cold molecules: Progress in Quantum Engineering of Chemistry and Quantum Matter text, January 2017

Phase-stabilized 100 mW frequency comb near 10 μm journal, June 2018

Time-resolved mid-infrared dual-comb spectroscopy journal, November 2019

Fast molecular fingerprinting with a coherent, rapidly tunable dual-comb spectrometer near 3 μm journal, January 2019

High-resolution infrared spectroscopy of jet cooled trans -deuteroxycarbonyl ( trans -DOCO) radical journal, May 2019

Spectral analyses of trans - and cis -DOCO transients via comb spectroscopy journal, June 2018

Direct observation of bimolecular reactions of ultracold KRb molecules journal, November 2019

Comb-resolved spectroscopy with immersion grating in long-wave infrared journal, January 2019

Roadmap on STIRAP applications text, January 2019

Roadmap on STIRAP applications other, January 2019

Roadmap on STIRAP applications journal, September 2019

Roadmap on STIRAP applications text, January 2019

Spectral analyses of trans- and cis-DOCO transients via comb spectroscopy text, January 2018

Comb-resolved spectroscopy with immersion grating in long-wave infrared text, January 2018

Roadmap on STIRAP applications text, January 2019

Phase-stabilized 100 mW frequency comb near 10 μm journal, June 2018

Time-resolved mid-infrared dual-comb spectroscopy journal, November 2019

Mid-Infrared Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals
journal, June 2014

Pure rotational spectra of the CO– trans -HOCO complex
journal, October 2012

Kinetics of the OH + CO reaction under atmospheric conditions
journal, January 1986

Kinetics of the reaction OH + CO under atmospheric conditions
journal, August 2001

Infrared Spectrum and Structure of Intermediates in the Reaction of OH with CO
journal, February 1971

Forward and reverse rate coefficients in equilibrating isomerization reactions
journal, April 1992

Reaction of HO with CO: Tunneling Is Indeed Important
journal, May 2012

Isotopic studies of trans- and cis- HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures
journal, March 2016

Reaction between hydroxyl (deuteroxyl) radicals and carbon monoxide at temperatures down to 80 K: experiment and theory
journal, November 1993

HOCO Radical Chemistry
journal, December 2010

Semiclassical transition state theory. A new perspective
journal, October 1993

Quantum dynamics of complex-forming bimolecular reactions
journal, January 2012

Modeling the Kinetics of Bimolecular Reactions
journal, November 2006

Energy and structure of the transition states in the reaction OH + CO ? H + CO2
journal, January 1991

High pressure range of the addition of HO to HO, NO, NO ₂ , and CO. I. Saturated laser induced fluorescence measurements at 298 K
journal, August 1995

High pressure range of addition reactions of HO. II. Temperature and pressure dependence of the reaction HO+CO⇔HOCO→H+CO ₂
journal, July 1996

Direct frequency comb measurement of OD + CO -> DOCO kinetics
journal, October 2016

Semi-classical theory for non-separable systems:. Construction of “good” action-angle variables for reaction rate constants
journal, January 1977

OD + CO → D + CO 2 branching kinetics probed with time-resolved frequency comb spectroscopy
journal, September 2017

Photolysis of the OC⋯HONO complex in low temperature matrices: Infrared detection and ab initio calculations of nitrosoformic acid, HOC(O)NO
journal, January 2003

Kinetics of OH(v= 0, 1) and OD(v= 0, 1) with CO and the mechanism of the OH + CO reaction
journal, January 1988

Molecular collisions, from warm to ultracold
journal, January 2009

Master Equation Analysis of Pressure-Dependent Atmospheric Reactions
journal, December 2003

Kinetic study of the reaction of OH with CO from 250 to 1040 K
journal, August 1983

Broadband Cavity Ringdown Spectroscopy for Sensitive and Rapid Molecular Detection
journal, March 2006

Pressure and temperature dependence of reactions proceeding via a bound complex. An approach for combustion and atmospheric chemistry modelers. Application to HO + CO ? [HOCO] ? H + CO2
journal, January 1988

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide
journal, October 2010

Observation of the pure rotational spectra of trans - and cis -HOCO
journal, May 2011

The HITRAN2012 molecular spectroscopic database
journal, November 2013

Molecular Transitions and Chemical Reaction Rates: The stochastic model relates the rate of a chemical reaction to the underlying transition probabilities
journal, June 1965

HO + CO Reaction Rates and H/D Kinetic Isotope Effects: Master Equation Models with ab Initio SCTST Rate Constants
journal, January 2013

Cold molecules: Progress in quantum engineering of chemistry and quantum matter
journal, September 2017

The pressure dependence of the rate constant of the reaction of OH radicals with CO
journal, January 1984

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics
journal, July 2004

The pressure dependence of the rate constant of the reaction of OD radicals with CO
journal, November 1982

PGOPHER: A program for simulating rotational, vibrational and electronic spectra
journal, January 2017

OH(OD) + CO: Measurements and an Optimized RRKM Fit
journal, October 1998

Modeling the Kinetics of Bimolecular Reactions
journal, January 2007

Cold molecules: Progress in Quantum Engineering of Chemistry and Quantum Matter
text, January 2017

Modeling the Kinetics of Bimolecular Reactions
journal, January 2007

HOCO Radical Chemistry
journal, December 2010

Master Equation Analysis of Pressure-Dependent Atmospheric Reactions
journal, December 2003

Molecular collisions, from warm to ultracold
journal, January 2009

Spectroscopy and dynamics of the HOCO radical: insights into the OH + CO → H + CO ₂ reaction
journal, January 2014

Observation of the pure rotational spectra of trans - and cis -HOCO
journal, May 2011

Pure rotational spectra of the CO– trans -HOCO complex
journal, October 2012

Isotopic studies of trans- and cis- HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures
journal, March 2016

Broadband Cavity Ringdown Spectroscopy for Sensitive and Rapid Molecular Detection
journal, March 2006

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide
journal, October 2010

Molecular Transitions and Chemical Reaction Rates: The stochastic model relates the rate of a chemical reaction to the underlying transition probabilities
journal, June 1965

Direct frequency comb measurement of OD + CO -> DOCO kinetics
journal, October 2016

Cold molecules: Progress in Quantum Engineering of Chemistry and Quantum Matter
text, January 2017

Phase-stabilized 100 mW frequency comb near 10 μm
journal, June 2018

Time-resolved mid-infrared dual-comb spectroscopy
journal, November 2019

Fast molecular fingerprinting with a coherent, rapidly tunable dual-comb spectrometer near 3 μm
journal, January 2019

High-resolution infrared spectroscopy of jet cooled trans -deuteroxycarbonyl ( trans -DOCO) radical
journal, May 2019

Spectral analyses of trans - and cis -DOCO transients via comb spectroscopy
journal, June 2018

Direct observation of bimolecular reactions of ultracold KRb molecules
journal, November 2019

Comb-resolved spectroscopy with immersion grating in long-wave infrared
journal, January 2019

Roadmap on STIRAP applications
text, January 2019

Roadmap on STIRAP applications
other, January 2019

Roadmap on STIRAP applications
journal, September 2019

Roadmap on STIRAP applications
text, January 2019

Spectral analyses of trans- and cis-DOCO transients via comb spectroscopy
text, January 2018

Comb-resolved spectroscopy with immersion grating in long-wave infrared
text, January 2018

Roadmap on STIRAP applications
text, January 2019

Phase-stabilized 100 mW frequency comb near 10 μm
journal, June 2018

Time-resolved mid-infrared dual-comb spectroscopy
journal, November 2019