Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

This content will become publicly available on Sun Aug 25 00:00:00 EDT 2024

Title: OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions

Abstract

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. Here this study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl ismore » shown to yield hydroxybutanone, and subsequent C–O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10–11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3];  [4];  [4]; ORCiD logo [4]; ORCiD logo [5];  [6]; ORCiD logo [6]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. University of Pennsylvania, Philadelphia, PA (United States)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Lab. (JPL); California Institute of Technology (CalTech), Pasadena, CA (United States)
  4. Sandia National Laboratory (SNL-CA), Livermore, CA (United States). Combustion Research Facility
  5. Sandia National Laboratory (SNL-CA), Livermore, CA (United States). Combustion Research Facility; University of California, Davis, CA (United States)
  6. California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Lab. (JPL)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Aeronautics and Space Administration (NASA); National Science Foundation (NSF)
OSTI Identifier:
2311457
Report Number(s):
SAND-2023-09007J
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
NA0003525; AC02-05CH11231; AC02-06CH11357; FG02-87ER13792; CHE-2102626; CHE190088; ACI-1548562; CHE-1955068; CHE-2301298
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 145; Journal Issue: 35; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkyls; energy; kinetics; photoionization; vinyl

Citation Formats

Liu, Tianlin, Elliott, Sarah N., Zou, Meijun, Vansco, Michael F., Sojdak, Christopher A., Markus, Charles R., Almeida, Raybel, Au, Kendrew, Sheps, Leonid, Osborn, David L., Winiberg, Frank F., Percival, Carl J., Taatjes, Craig A., Caravan, Rebecca L., Klippenstein, Stephen J., and Lester, Marsha I. OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions. United States: N. p., 2023. Web. doi:10.1021/jacs.3c07126.
Copy to clipboard
Liu, Tianlin, Elliott, Sarah N., Zou, Meijun, Vansco, Michael F., Sojdak, Christopher A., Markus, Charles R., Almeida, Raybel, Au, Kendrew, Sheps, Leonid, Osborn, David L., Winiberg, Frank F., Percival, Carl J., Taatjes, Craig A., Caravan, Rebecca L., Klippenstein, Stephen J., & Lester, Marsha I. OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions. United States. https://doi.org/10.1021/jacs.3c07126
Copy to clipboard
Liu, Tianlin, Elliott, Sarah N., Zou, Meijun, Vansco, Michael F., Sojdak, Christopher A., Markus, Charles R., Almeida, Raybel, Au, Kendrew, Sheps, Leonid, Osborn, David L., Winiberg, Frank F., Percival, Carl J., Taatjes, Craig A., Caravan, Rebecca L., Klippenstein, Stephen J., and Lester, Marsha I. Fri . "OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions". United States. https://doi.org/10.1021/jacs.3c07126.
Copy to clipboard
@article{osti_2311457,
title = {OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions},
author = {Liu, Tianlin and Elliott, Sarah N. and Zou, Meijun and Vansco, Michael F. and Sojdak, Christopher A. and Markus, Charles R. and Almeida, Raybel and Au, Kendrew and Sheps, Leonid and Osborn, David L. and Winiberg, Frank F. and Percival, Carl J. and Taatjes, Craig A. and Caravan, Rebecca L. and Klippenstein, Stephen J. and Lester, Marsha I.},
abstractNote = {Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. Here this study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C–O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10–11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).},
doi = {10.1021/jacs.3c07126},
journal = {Journal of the American Chemical Society},
number = 35,
volume = 145,
place = {United States},
year = {Fri Aug 25 00:00:00 EDT 2023},
month = {Fri Aug 25 00:00:00 EDT 2023}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
This content will become publicly available on August 25, 2024
Publisher's Version of Record
https://doi.org/10.1021/jacs.3c07126
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Measurement and modelling of air pollution and atmospheric chemistry in the U.K. West Midlands conurbation: Overview of the PUMA Consortium project
journal, May 2006

UV Spectroscopic Characterization of Dimethyl- and Ethyl-Substituted Carbonyl Oxides
journal, March 2014

  • Liu, Fang; Beames, Joseph M.; Green, Amy M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 12
  • DOI: 10.1021/jp412726z

Variational optimizations in the Rice–Ramsperger–Kassel–Marcus theory calculations for unimolecular dissociations with no reverse barrier
journal, January 1992

  • Klippenstein, Stephen J.
  • The Journal of Chemical Physics, Vol. 96, Issue 1
  • DOI: 10.1063/1.462472

Criegee intermediates: production, detection and reactivity
journal, July 2020

  • Chhantyal-Pun, Rabi; Khan, M. Anwar H.; Taatjes, Craig A.
  • International Reviews in Physical Chemistry, Vol. 39, Issue 3
  • DOI: 10.1080/0144235X.2020.1792104

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2
journal, October 2023

  • Zou, Meijun; Liu, Tianlin; Vansco, Michael F.
  • The Journal of Physical Chemistry A, Vol. 127, Issue 43
  • DOI: 10.1021/acs.jpca.3c04648

Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products
journal, April 2016

  • Kidwell, Nathanael M.; Li, Hongwei; Wang, Xiaohong
  • Nature Chemistry, Vol. 8, Issue 5
  • DOI: 10.1038/nchem.2488

2,3-Dimethyl-2-butene (TME) Ozonolysis: Pressure Dependence of Stabilized Criegee Intermediates and Evidence of Stabilized Vinyl Hydroperoxides
journal, January 2011

  • Drozd, Greg T.; Kroll, Jesse; Donahue, Neil M.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 2
  • DOI: 10.1021/jp108773d

Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years
journal, January 2014

  • Sindelarova, K.; Granier, C.; Bouarar, I.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 17
  • DOI: 10.5194/acp-14-9317-2014

The ezSpectra suite: An easy‐to‐use toolkit for spectroscopy modeling
journal, May 2021

  • Gozem, Samer; Krylov, Anna I.
  • WIREs Computational Molecular Science
  • DOI: 10.1002/wcms.1546

NIST Chemistry WebBook, NIST Standard Reference Database 69
dataset, January 1997

  • Linstrom, Peter
  • National Institute of Standards and Technology
  • DOI: 10.18434/T4D303

Vacuum ultraviolet photoionization cross section of the hydroxyl radical
journal, May 2018

  • Dodson, Leah G.; Savee, John D.; Gozem, Samer
  • The Journal of Chemical Physics, Vol. 148, Issue 18
  • DOI: 10.1063/1.5024249

Mechanism of HO x Formation in the Gas-Phase Ozone-Alkene Reaction. 2. Prompt versus Thermal Dissociation of Carbonyl Oxides to Form OH
journal, May 2001

  • Kroll, Jesse H.; Sahay, Shailesh R.; Anderson, James G.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 18
  • DOI: 10.1021/jp004136v

Rotationally resolved threshold photoelectron spectra of OH and OD
journal, July 1992

  • Wiedmann, R. T.; Tonkyn, R. G.; White, M. G.
  • The Journal of Chemical Physics, Vol. 97, Issue 2
  • DOI: 10.1063/1.463179

Unimolecular Decay of the Dimethyl-Substituted Criegee Intermediate in Alkene Ozonolysis: Decay Time Scales and the Importance of Tunneling
journal, August 2017

  • Drozd, Greg T.; Kurtén, Theo; Donahue, Neil M.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 32
  • DOI: 10.1021/acs.jpca.7b05495

VUV Photoionization Cross Sections of HO 2 , H 2 O 2 , and H 2 CO
journal, February 2015

  • Dodson, Leah G.; Shen, Linhan; Savee, John D.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 8
  • DOI: 10.1021/jp508942a

Current Status of Transition-State Theory
journal, January 1996

  • Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953748q

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH 3 ) 2 COO
journal, December 2016

  • Chhantyal-Pun, Rabi; Welz, Oliver; Savee, John D.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 1
  • DOI: 10.1021/acs.jpca.6b07810

Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes
journal, March 2018

The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere
journal, January 2008

  • Johnson, David; Marston, George
  • Chemical Society Reviews, Vol. 37, Issue 4
  • DOI: 10.1039/b704260b

MRCISD Studies of the Dissociation of Vinylhydroperoxide, CH 2 CHOOH: There Is a Saddle Point
journal, May 2012

  • Kurtén, Theo; Donahue, Neil M.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 25
  • DOI: 10.1021/jp302511a

Direct Kinetic Measurements of Criegee Intermediate (CH2OO) Formed by Reaction of CH2I with O2
journal, January 2012

Statistical Theory for the Kinetics and Dynamics of Roaming Reactions
journal, December 2011

  • Klippenstein, Stephen J.; Georgievskii, Yuri; Harding, Lawrence B.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 50
  • DOI: 10.1021/jp208347j

Atmospheric chemistry of olefins: a product study of the ozone-alkene reaction with cyclohexane added to scavenge hydroxyl radical
journal, January 1994

  • Grosjean, Daniel.; Grosjean, Eric.; Williams, Edwin L.
  • Environmental Science & Technology, Vol. 28, Issue 1
  • DOI: 10.1021/es00050a026

Absolute Photoionization Cross Section of the Simplest Enol, Vinyl Alcohol
journal, September 2021

  • Rösch, Daniel; Caravan, Rebecca L.; Taatjes, Craig A.
  • The Journal of Physical Chemistry A, Vol. 125, Issue 36
  • DOI: 10.1021/acs.jpca.1c05825

Formation of dimethylketene and methacrolein by reaction of the CH radical with acetone
journal, January 2013

  • Goulay, Fabien; Derakhshan, Adeeb; Maher, Eamonn
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 11
  • DOI: 10.1039/c3cp43829e

Roaming Reactions and Dynamics in the van der Waals Region
journal, April 2020

The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics
journal, October 2008

  • Osborn, David L.; Zou, Peng; Johnsen, Howard
  • Review of Scientific Instruments, Vol. 79, Issue 10
  • DOI: 10.1063/1.3000004

Quantum Chemical and Statistical Rate Theory Studies of the Vinyl Hydroperoxides Formed in trans -2-Butene and 2,3-Dimethyl-2-butene Ozonolysis
journal, February 2018

  • Kuwata, Keith T.; Luu, Lina; Weberg, Alexander B.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 9
  • DOI: 10.1021/acs.jpca.8b00287

Transition State Theory for Multichannel Addition Reactions:  Multifaceted Dividing Surfaces
journal, November 2003

  • Georgievskii, Yuri; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 46
  • DOI: 10.1021/jp034564b

Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production
journal, July 2018

  • Barber, Victoria P.; Pandit, Shubhrangshu; Green, Amy M.
  • Journal of the American Chemical Society, Vol. 140, Issue 34
  • DOI: 10.1021/jacs.8b06010

Substituent Effects on the Electronic Spectroscopy of Four-Carbon Criegee Intermediates
journal, September 2022

  • Liu, Tianlin; Zou, Meijun; Caracciolo, Adriana
  • The Journal of Physical Chemistry A, Vol. 126, Issue 38
  • DOI: 10.1021/acs.jpca.2c05502

Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact
journal, December 2019

Probing the conformational behavior of the doubly substituted methyl-ethyl Criegee intermediate by FTMW spectroscopy
journal, May 2017

  • Cabezas, Carlos; Guillemin, Jean-Claude; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 146, Issue 17
  • DOI: 10.1063/1.4982682

Mechanism of HO x Formation in the Gas-Phase Ozone−Alkene Reaction. 1. Direct, Pressure-Dependent Measurements of Prompt OH Yields †
journal, March 2001

  • Kroll, Jesse H.; Clarke, James S.; Donahue, Neil M.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 9
  • DOI: 10.1021/jp002121r

Determination of the Absolute Photoionization Cross Sections of CH 3 and I Produced from a Pyrolysis Source, by Combined Synchrotron and Vacuum Ultraviolet Laser Studies †
journal, March 2010

  • Gans, Bérenger; Mendes, Luiz A. Vieira; Boyé-Péronne, Séverine
  • The Journal of Physical Chemistry A, Vol. 114, Issue 9
  • DOI: 10.1021/jp909414d

Adventures in ozoneland: down the rabbit-hole
journal, January 2011

  • Donahue, Neil M.; Drozd, Greg T.; Epstein, Scott A.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 23
  • DOI: 10.1039/c0cp02564j

Roaming Pathway Leading to Unexpected Water + Vinyl Products in C 2 H 4 OH Dissociation
journal, October 2010

  • Kamarchik, Eugene; Koziol, Lucas; Reisler, Hanna
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 20
  • DOI: 10.1021/jz1011884

The physical chemistry of Criegee intermediates in the gas phase
journal, July 2015

Absolute photoionization cross-sections of some combustion intermediates
journal, January 2012

Experimental and theoretical studies of the doubly substituted methyl-ethyl Criegee intermediate: Infrared action spectroscopy and unimolecular decay to OH radical products
journal, March 2020

  • Barber, Victoria P.; Hansen, Anne S.; Georgievskii, Yuri
  • The Journal of Chemical Physics, Vol. 152, Issue 9
  • DOI: 10.1063/5.0002422

Unimolecular decay strongly limits the atmospheric impact of Criegee intermediates
journal, January 2017

  • Vereecken, L.; Novelli, A.; Taraborrelli, D.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 47
  • DOI: 10.1039/C7CP05541B

Oxidation of hydrazones with iodine in the presence of base
journal, January 1970

  • Pross, A.; Sternhell, S.
  • Australian Journal of Chemistry, Vol. 23, Issue 5
  • DOI: 10.1071/CH9700989

Open questions on the reactivity of Criegee intermediates
journal, March 2021

  • Caravan, Rebecca L.; Vansco, Michael F.; Lester, Marsha I.
  • Communications Chemistry, Vol. 4, Issue 1
  • DOI: 10.1038/s42004-021-00483-5

FTIR spectroscopic study of the mechanism for the gas-phase reaction between ozone and tetramethylethylene
journal, February 1987

  • Niki, H.; Maker, P. D.; Savage, C. M.
  • The Journal of Physical Chemistry, Vol. 91, Issue 4
  • DOI: 10.1021/j100288a035

Influence of oxygenation in cyclic hydrocarbons on chain-termination reactions from R + O2: tetrahydropyran and cyclohexane
journal, January 2017

  • Rotavera, Brandon; Savee, John D.; Antonov, Ivan O.
  • Proceedings of the Combustion Institute, Vol. 36, Issue 1
  • DOI: 10.1016/j.proci.2016.05.020

Hydroxyacetone Production From C 3 Criegee Intermediates
journal, December 2016

  • Taatjes, Craig A.; Liu, Fang; Rotavera, Brandon
  • The Journal of Physical Chemistry A, Vol. 121, Issue 1
  • DOI: 10.1021/acs.jpca.6b07712

Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO
journal, April 2013

Isotope Effects in the Photoionization Yields and the Absorption Cross Sections for Acetylene, Propyne, and Propene
journal, September 1970

  • Person, James C.; Nicole, Paul P.
  • The Journal of Chemical Physics, Vol. 53, Issue 5
  • DOI: 10.1063/1.1674254

Master Equation Methods in Gas Phase Chemical Kinetics
journal, September 2006

  • Miller, James A.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 36
  • DOI: 10.1021/jp062693x

Low-temperature combustion chemistry of biofuels: pathways in the initial low-temperature (550 K–750 K) oxidation chemistry of isopentanol
journal, January 2012

  • Welz, Oliver; Zádor, Judit; Savee, John D.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 9
  • DOI: 10.1039/c2cp23248k

From the Time-Dependent, Multiple-Well Master Equation to Phenomenological Rate Coefficients
journal, October 2002

  • Klippenstein, Stephen J.; Miller, James A.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 40
  • DOI: 10.1021/jp021175t

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates
journal, November 2020

  • Cox, R. Anthony; Ammann, Markus; Crowley, John N.
  • Atmospheric Chemistry and Physics, Vol. 20, Issue 21
  • DOI: 10.5194/acp-20-13497-2020
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: