Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

Fang, Yi; Liu, Fang; Barber, Victoria P.; Klippenstein, Stephen J.; McCoy, Anne B.; Lester, Marsha I.

doi:10.1063/1.4941768

Title: Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

Journal Article · Wed Feb 10 00:00:00 EST 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4941768· OSTI ID:1350086

Fang, Yi ^[1];

^[1]; Barber, Victoria P. ^[1]; Klippenstein, Stephen J. ^[2]; McCoy, Anne B. ^[3]; Lester, Marsha I. ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

In the atmosphere, a dominant loss process for carbonyl oxide intermediates produced from alkene ozonolysis is also an important source of hydroxyl radicals. In this work, the rate of appearance of OH radicals is revealed through direct time-domain measurements following vibrational activation of prototypical methyl-substituted Criegee intermediates under collision-free conditions. Complementary theoretical calculations predict the unimolecular decay rate for the Criegee intermediates in the vicinity of the barrier for 1,4 hydrogen transfer that leads to OH products. Both experiment and theory yield unimolecular decay rates of ca. 10⁸ and 10⁷ s^–1 for syn-CH₃CHOO and (CH₃)₂COO, respectively, at energies near the barrier. Tunneling through the barrier, computed from high level electronic structure theory and experimentally validated, makes a significant contribution to the decay rate. Extension to thermally averaged unimolecular decay of stabilized Criegee intermediates under atmospheric conditions yields rates that are six orders of magnitude slower than those evaluated directly in the barrier region.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-06CH11357; CHE-1362835; CHE-1465001; CHE-1213347

OSTI ID:: 1350086

Alternate ID(s):: OSTI ID: 1237774

Journal Information:: Journal of Chemical Physics, Vol. 144, Issue 6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 27 works

Citation information provided by
Web of Science

References (28)

Simplified CCSD(T)-F12 methods: Theory and benchmarks Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 130, Issue 5 https://doi.org/10.1063/1.3054300	journal	February 2009
Measurement of Absolute Unimolecular and Bimolecular Rate Constants for CH ₃ CHOO Generated by the trans -2-Butene Reaction with Ozone in the Gas Phase Fenske, Jill D.; Hasson, Alam S.; Ho, Andy W. The Journal of Physical Chemistry A, Vol. 104, Issue 44 https://doi.org/10.1021/jp0016636	journal	November 2000
Direct observation of OH formation from stabilised Criegee intermediates Novelli, A.; Vereecken, L.; Lelieveld, J. Phys. Chem. Chem. Phys., Vol. 16, Issue 37 https://doi.org/10.1039/C4CP02719A	journal	January 2014
Measurement and modelling of air pollution and atmospheric chemistry in the U.K. West Midlands conurbation: Overview of the PUMA Consortium project Harrison, R. M.; Yin, J.; Tilling, R. M. Science of The Total Environment, Vol. 360, Issue 1-3 https://doi.org/10.1016/j.scitotenv.2005.08.053	journal	May 2006
UV Spectroscopic Characterization of Dimethyl- and Ethyl-Substituted Carbonyl Oxides Liu, Fang; Beames, Joseph M.; Green, Amy M. The Journal of Physical Chemistry A, Vol. 118, Issue 12 https://doi.org/10.1021/jp412726z	journal	March 2014
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon Woon, David E.; Dunning, Thom H. The Journal of Chemical Physics, Vol. 103, Issue 11 https://doi.org/10.1063/1.470645	journal	September 1995
W4-11: A high-confidence benchmark dataset for computational thermochemistry derived from first-principles W4 data Karton, Amir; Daon, Shauli; Martin, Jan M. L. Chemical Physics Letters, Vol. 510, Issue 4-6 https://doi.org/10.1016/j.cplett.2011.05.007	journal	July 2011
Computational Studies of the Isomerization and Hydration Reactions of Acetaldehyde Oxide and Methyl Vinyl Carbonyl Oxide Kuwata, Keith T.; Hermes, Matthew R.; Carlson, Matthew J. The Journal of Physical Chemistry A, Vol. 114, Issue 34 https://doi.org/10.1021/jp105358v	journal	September 2010
UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH ₃ CHOO Beames, Joseph M.; Liu, Fang; Lu, Lu The Journal of Chemical Physics, Vol. 138, Issue 24 https://doi.org/10.1063/1.4810865	journal	June 2013
Stabilization of the Simplest Criegee Intermediate from the Reaction between Ozone and Ethylene: A High-Level Quantum Chemical and Kinetic Analysis of Ozonolysis Nguyen, Thanh Lam; Lee, Hyunwoo; Matthews, Devin A. The Journal of Physical Chemistry A, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpca.5b02088	journal	May 2015
Ultraviolet Spectrum and Photochemistry of the Simplest Criegee Intermediate CH ₂ OO Beames, Joseph M.; Liu, Fang; Lu, Lu Journal of the American Chemical Society, Vol. 134, Issue 49 https://doi.org/10.1021/ja310603j	journal	December 2012
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Adventures in ozoneland: down the rabbit-hole Donahue, Neil M.; Drozd, Greg T.; Epstein, Scott A. Physical Chemistry Chemical Physics, Vol. 13, Issue 23 https://doi.org/10.1039/c0cp02564j	journal	January 2011
The physical chemistry of Criegee intermediates in the gas phase Osborn, David L.; Taatjes, Craig A. International Reviews in Physical Chemistry, Vol. 34, Issue 3 https://doi.org/10.1080/0144235X.2015.1055676	journal	July 2015
Mechanism of HO _x Formation in the Gas-Phase Ozone-Alkene Reaction. 2. Prompt versus Thermal Dissociation of Carbonyl Oxides to Form OH Kroll, Jesse H.; Sahay, Shailesh R.; Anderson, James G. The Journal of Physical Chemistry A, Vol. 105, Issue 18 https://doi.org/10.1021/jp004136v	journal	May 2001
Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂ Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min Proceedings of the National Academy of Sciences, Vol. 112, Issue 35 https://doi.org/10.1073/pnas.1513149112	journal	August 2015
Night-time radical chemistry during the TORCH campaign Emmerson, K. M.; Carslaw, N. Atmospheric Environment, Vol. 43, Issue 20 https://doi.org/10.1016/j.atmosenv.2009.03.042	journal	June 2009
Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar Peterson, Kirk A.; Adler, Thomas B.; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 128, Issue 8 https://doi.org/10.1063/1.2831537	journal	February 2008
High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview Harding, Michael E.; Vázquez, Juana; Ruscic, Branko The Journal of Chemical Physics, Vol. 128, Issue 11 https://doi.org/10.1063/1.2835612	journal	March 2008
Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO Taatjes, C. A.; Welz, O.; Eskola, A. J. Science, Vol. 340, Issue 6129 https://doi.org/10.1126/science.1234689	journal	April 2013
Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products Liu, F.; Beames, J. M.; Petit, A. S. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1257158	journal	September 2014
Decomposition pathways of the excited Criegee intermediates in the ozonolysis of simple alkenes Horie, O.; Moortgat, G. K. Atmospheric Environment. Part A. General Topics, Vol. 25, Issue 9 https://doi.org/10.1016/0960-1686(91)90271-8	journal	January 1991
The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere Johnson, David; Marston, George Chemical Society Reviews, Vol. 37, Issue 4 https://doi.org/10.1039/b704260b	journal	January 2008
Direct Kinetic Measurements of Criegee Intermediate (CH2OO) Formed by Reaction of CH2I with O2 Welz, O.; Savee, J. D.; Osborn, D. L. Science, Vol. 335, Issue 6065 https://doi.org/10.1126/science.1213229	journal	January 2012
Direct production of OH radicals upon CH overtone activation of (CH ₃ ) ₂ COO Criegee intermediates Liu, Fang; Beames, Joseph M.; Lester, Marsha I. The Journal of Chemical Physics, Vol. 141, Issue 23 https://doi.org/10.1063/1.4903961	journal	December 2014
Master Equation Methods in Gas Phase Chemical Kinetics Miller, James A.; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 110, Issue 36 https://doi.org/10.1021/jp062693x	journal	September 2006
Free radical modelling studies during the UK TORCH Campaign in Summer 2003 Emmerson, K. M.; Carslaw, N.; Carslaw, D. C. Atmospheric Chemistry and Physics, Vol. 7, Issue 1 https://doi.org/10.5194/acp-7-167-2007	journal	January 2007
Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO ₂ , H ₂ O and decomposition under boundary layer conditions Newland, Mike J.; Rickard, Andrew R.; Alam, Mohammed S. Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP04186K	journal	January 2015

Cited By (22)

Theoretical Study of the Reaction of Carbonyl Oxide with Nitrogen Dioxide: CH ₂ OO + NO ₂ : THEORETICAL STUDY OF THE REACTION OF CARBONYL OXIDE WITH NITROGEN DIOXIDE Vereecken, L.; Nguyen, H. M. T. International Journal of Chemical Kinetics, Vol. 49, Issue 10 https://doi.org/10.1002/kin.21112	journal	August 2017
Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products Kidwell, Nathanael M.; Li, Hongwei; Wang, Xiaohong Nature Chemistry, Vol. 8, Issue 5 https://doi.org/10.1038/nchem.2488	journal	April 2016
Temperature dependence of the reaction of anti-CH ₃ CHOO with water vapor Lin, Liang-Chun; Chao, Wen; Chang, Chun-Hung Physical Chemistry Chemical Physics, Vol. 18, Issue 40 https://doi.org/10.1039/c6cp05171e	journal	January 2016
Adaptive free energy sampling in multidimensional collective variable space using boxed molecular dynamics O'Connor, Mike; Paci, Emanuele; McIntosh-Smith, Simon Faraday Discuss., Vol. 195 https://doi.org/10.1039/c6fd00138f	journal	January 2016
Reactions between hydroxyl-substituted alkylperoxy radicals and Criegee intermediates: correlations of the electronic characteristics of methyl substituents and the reactivity Zhao, Qiangli; Liu, Fengyi; Wang, Weina Physical Chemistry Chemical Physics, Vol. 19, Issue 23 https://doi.org/10.1039/c7cp00869d	journal	January 2017
Criegee intermediates and their impacts on the troposphere Khan, M. A. H.; Percival, C. J.; Caravan, R. L. Environmental Science: Processes & Impacts, Vol. 20, Issue 3 https://doi.org/10.1039/c7em00585g	journal	January 2018
The reaction between the methyl Criegee intermediate and hydrogen chloride: an FTMW spectroscopic study Cabezas, Carlos; Endo, Yasuki Physical Chemistry Chemical Physics, Vol. 20, Issue 35 https://doi.org/10.1039/c8cp04171g	journal	January 2018
Experimental and computational studies of Criegee intermediate reactions with NH ₃ and CH ₃ NH ₂ Chhantyal-Pun, Rabi; Shannon, Robin J.; Tew, David P. Physical Chemistry Chemical Physics, Vol. 21, Issue 26 https://doi.org/10.1039/c8cp06810k	journal	January 2019
Observation of hydroperoxyethyl formate from the reaction between the methyl Criegee intermediate and formic acid Cabezas, Carlos; Endo, Yasuki Physical Chemistry Chemical Physics, Vol. 22, Issue 2 https://doi.org/10.1039/c9cp05030b	journal	January 2020
Direct observation of unimolecular decay of CH ₃ CH ₂ CHOO Criegee intermediates to OH radical products Fang, Yi; Liu, Fang; Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 145, Issue 4 https://doi.org/10.1063/1.4958992	journal	July 2016
Communication: Thermal unimolecular decomposition of syn-CH ₃ CHOO: A kinetic study Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C. The Journal of Chemical Physics, Vol. 145, Issue 13 https://doi.org/10.1063/1.4964393	journal	October 2016
Deep tunneling in the unimolecular decay of CH ₃ CHOO Criegee intermediates to OH radical products Fang, Yi; Liu, Fang; Barber, Victoria P. The Journal of Chemical Physics, Vol. 145, Issue 23 https://doi.org/10.1063/1.4972015	journal	December 2016
Conformational analysis of ethyl-substituted Criegee intermediate by FTMW spectroscopy Cabezas, Carlos; Guillemin, Jean-Claude; Endo, Yasuki The Journal of Chemical Physics, Vol. 145, Issue 22 https://doi.org/10.1063/1.4972017	journal	December 2016
Tunneling effects in the unimolecular decay of (CH ₃ ) ₂ COO Criegee intermediates to OH radical products Fang, Yi; Barber, Victoria P.; Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 146, Issue 13 https://doi.org/10.1063/1.4979297	journal	April 2017
The reactivity of the Criegee intermediate CH ₃ CHOO with water probed by FTMW spectroscopy Cabezas, Carlos; Endo, Yasuki The Journal of Chemical Physics, Vol. 148, Issue 1 https://doi.org/10.1063/1.5009033	journal	January 2018
Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis Vansco, Michael F.; Marchetti, Barbara; Lester, Marsha I. The Journal of Chemical Physics, Vol. 149, Issue 24 https://doi.org/10.1063/1.5064716	journal	December 2018
Characterization of the 2-methylvinoxy radical + O ₂ reaction: A focal point analysis and composite multireference study Davis, Matthew M.; Weidman, Jared D.; Abbott, Adam S. The Journal of Chemical Physics, Vol. 151, Issue 12 https://doi.org/10.1063/1.5113800	journal	September 2019
Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products Green, Amy M.; Barber, Victoria P.; Fang, Yi Proceedings of the National Academy of Sciences, Vol. 114, Issue 47 https://doi.org/10.1073/pnas.1715014114	journal	November 2017
Unimolecular reaction of acetone oxide and its reaction with water in the atmosphere Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G. Proceedings of the National Academy of Sciences, Vol. 115, Issue 24 https://doi.org/10.1073/pnas.1804453115	journal	May 2018
Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact Stephenson, Thomas A.; Lester, Marsha I. International Reviews in Physical Chemistry, Vol. 39, Issue 1 https://doi.org/10.1080/0144235x.2020.1688530	journal	December 2019
Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument Novelli, Anna; Hens, Korbinian; Tatum Ernest, Cheryl Atmospheric Chemistry and Physics, Vol. 17, Issue 12 https://doi.org/10.5194/acp-17-7807-2017	journal	January 2017
The atmospheric impacts of monoterpene ozonolysis on global stabilised Criegee intermediate budgets and SO ₂ oxidation: experiment, theory and modelling Newland, Mike J.; Rickard, Andrew R.; Sherwen, Tomás Atmospheric Chemistry and Physics, Vol. 18, Issue 8 https://doi.org/10.5194/acp-18-6095-2018	journal	January 2018

Similar Records

Direct observation of unimolecular decay of CH₃CH₂CHOO Criegee intermediates to OH radical products

Journal Article · Wed Jul 27 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1350086

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.; +1 more

Deep tunneling in the unimolecular decay of CH₃CHOO Criegee intermediates to OH radical products

Journal Article · Mon Dec 19 00:00:00 EST 2016 · Journal of Chemical Physics · OSTI ID:1350086

Fang, Yi; Liu, Fang; Barber, Victoria P.; +3 more

Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

Journal Article · Thu Jul 28 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1350086

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
RRKM Theory
criegee intermediate
theoretical kinetics
unimolecular

Title: Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

Citation Formats

References (28)

Cited By (22)

Similar Records

Related Subjects