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Title: Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry

Abstract

Elucidating atmospheric oxidation mechanisms is necessary for estimating the lifetimes of atmospheric species and understanding secondary organic aerosol formation and atmospheric oxidation capacity. We report an unexpectedly fast mechanistic pathway for the unimolecular reactions of large stabilized Criegee intermediates, which involves the formation of bicyclic structures from large Criegee intermediates containing an aldehyde group. The barrier heights of the mechanistic pathways are unexpectedly low – about 2–3 kcal/mol – and are at least 10 kcal/mol lower than those of hydrogen shift processes in large syn Criegee intermediates; and the calculated rate constants show that the mechanistic pathways are 10 5-10 9 times faster than those of the corresponding hydrogen shift processes. The present findings indicate that analogous low-energy pathways can now also be expected in other large Criegee intermediates and that oxidative capacity of some Criegee intermediates is smaller than would be predicted by existing models.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Guizhou Minzu Univ., Guiyang (China). School of Materials Science and Engineering; Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst.; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center
  2. Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst.; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE
OSTI Identifier:
1527371
Grant/Contract Number:  
SC0015997
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES

Citation Formats

Long, Bo, Bao, Junwei Lucas, and Truhlar, Donald G. Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry. United States: N. p., 2019. Web. doi:10.1038/s41467-019-09948-7.
Long, Bo, Bao, Junwei Lucas, & Truhlar, Donald G. Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry. United States. doi:10.1038/s41467-019-09948-7.
Long, Bo, Bao, Junwei Lucas, and Truhlar, Donald G. Wed . "Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry". United States. doi:10.1038/s41467-019-09948-7. https://www.osti.gov/servlets/purl/1527371.
@article{osti_1527371,
title = {Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry},
author = {Long, Bo and Bao, Junwei Lucas and Truhlar, Donald G.},
abstractNote = {Elucidating atmospheric oxidation mechanisms is necessary for estimating the lifetimes of atmospheric species and understanding secondary organic aerosol formation and atmospheric oxidation capacity. We report an unexpectedly fast mechanistic pathway for the unimolecular reactions of large stabilized Criegee intermediates, which involves the formation of bicyclic structures from large Criegee intermediates containing an aldehyde group. The barrier heights of the mechanistic pathways are unexpectedly low – about 2–3 kcal/mol – and are at least 10 kcal/mol lower than those of hydrogen shift processes in large syn Criegee intermediates; and the calculated rate constants show that the mechanistic pathways are 105-109 times faster than those of the corresponding hydrogen shift processes. The present findings indicate that analogous low-energy pathways can now also be expected in other large Criegee intermediates and that oxidative capacity of some Criegee intermediates is smaller than would be predicted by existing models.},
doi = {10.1038/s41467-019-09948-7},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {5}
}

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Works referenced in this record:

MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids
journal, February 2016

  • Yu, Haoyu S.; He, Xiao; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 3
  • DOI: 10.1021/acs.jctc.5b01082

Criegee intermediates and their impacts on the troposphere
journal, January 2018

  • Khan, M. A. H.; Percival, C. J.; Caravan, R. L.
  • Environmental Science: Processes & Impacts, Vol. 20, Issue 3
  • DOI: 10.1039/C7EM00585G

The reactions of Criegee intermediates with alkenes, ozone, and carbonyl oxides
journal, January 2014

  • Vereecken, L.; Harder, H.; Novelli, A.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 9
  • DOI: 10.1039/c3cp54514h

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

Quantum Thermochemistry: Multistructural Method with Torsional Anharmonicity Based on a Coupled Torsional Potential
journal, February 2013

  • Zheng, Jingjing; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 3
  • DOI: 10.1021/ct3010722

Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries
journal, August 2010

  • Alecu, I. M.; Zheng, Jingjing; Zhao, Yan
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 9
  • DOI: 10.1021/ct100326h

Mechanism of Gas-Phase Ozonolysis of β-Myrcene in the Atmosphere
journal, February 2018

  • Deng, Peng; Wang, Lingyu; Wang, Liming
  • The Journal of Physical Chemistry A, Vol. 122, Issue 11
  • DOI: 10.1021/acs.jpca.8b00983

New particle formation in the free troposphere: A question of chemistry and timing
journal, May 2016


Computational Studies of the Isomerization and Hydration Reactions of Acetaldehyde Oxide and Methyl Vinyl Carbonyl Oxide
journal, September 2010

  • Kuwata, Keith T.; Hermes, Matthew R.; Carlson, Matthew J.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 34
  • DOI: 10.1021/jp105358v

Molecular modeling of the kinetic isotope effect for the [1,5]-sigmatropic rearrangement of cis-1,3-pentadiene
journal, March 1993

  • Liu, Yi Ping; Lynch, Gillian C.; Truong, Thanh N.
  • Journal of the American Chemical Society, Vol. 115, Issue 6
  • DOI: 10.1021/ja00059a041

Ultraviolet Spectrum and Photochemistry of the Simplest Criegee Intermediate CH 2 OO
journal, December 2012

  • Beames, Joseph M.; Liu, Fang; Lu, Lu
  • Journal of the American Chemical Society, Vol. 134, Issue 49
  • DOI: 10.1021/ja310603j

Theoretical Chemical Kinetics in Tropospheric Chemistry: Methodologies and Applications
journal, February 2015

  • Vereecken, Luc; Glowacki, David R.; Pilling, Michael J.
  • Chemical Reviews, Vol. 115, Issue 10
  • DOI: 10.1021/cr500488p

How does substitution affect the unimolecular reaction rates of Criegee intermediates?
journal, January 2017

  • Yin, Cangtao; Takahashi, Kaito
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 19
  • DOI: 10.1039/C7CP01091E

Mechanism of Ozonolysis
journal, November 1975

  • Criegee, Rudolf
  • Angewandte Chemie International Edition in English, Vol. 14, Issue 11
  • DOI: 10.1002/anie.197507451

Quantum Chemical and Master Equation Studies of the Methyl Vinyl Carbonyl Oxides Formed in Isoprene Ozonolysis
journal, December 2005

  • Kuwata, Keith T.; Valin, Lukas C.; Converse, Amber D.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 47
  • DOI: 10.1021/jp054346d

The atmospheric impacts of monoterpene ozonolysis on global stabilised Criegee intermediate budgets and SO 2 oxidation: experiment, theory and modelling
journal, January 2018

  • Newland, Mike J.; Rickard, Andrew R.; Sherwen, Tomás
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 8
  • DOI: 10.5194/acp-18-6095-2018

The role of low-volatility organic compounds in initial particle growth in the atmosphere
journal, May 2016

  • Tröstl, Jasmin; Chuang, Wayne K.; Gordon, Hamish
  • Nature, Vol. 533, Issue 7604
  • DOI: 10.1038/nature18271

Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review
journal, January 2003


Gas-phase oxidation of sulfur dioxide in the ozone-olefin reactions
journal, September 1984

  • Hatakeyama, Shiro; Kobayashi, Hiroshi; Akimoto, Hajime
  • The Journal of Physical Chemistry, Vol. 88, Issue 20
  • DOI: 10.1021/j150664a058

Kinetics of Hydrogen Radical Reactions with Toluene Including Chemical Activation Theory Employing System-Specific Quantum RRK Theory Calibrated by Variational Transition State Theory
journal, February 2016

  • Bao, Junwei Lucas; Zheng, Jingjing; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11938

Extrapolation of high-order correlation energies: the WMS model
journal, January 2018

  • Zhao, Yan; Xia, Lixue; Liao, Xiaobin
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 43
  • DOI: 10.1039/C8CP04973D

Theoretical study on the detailed reaction mechanisms of carbonyl oxide with formic acid
journal, December 2009


Rapid Autoxidation Forms Highly Oxidized RO 2 Radicals in the Atmosphere
journal, October 2014

  • Jokinen, Tuija; Sipilä, Mikko; Richters, Stefanie
  • Angewandte Chemie International Edition, Vol. 53, Issue 52
  • DOI: 10.1002/anie.201408566

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

The DBH24/08 Database and Its Use to Assess Electronic Structure Model Chemistries for Chemical Reaction Barrier Heights
journal, March 2009

  • Zheng, Jingjing; Zhao, Yan; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 4
  • DOI: 10.1021/ct800568m

A new atmospherically relevant oxidant of sulphur dioxide
journal, August 2012

  • Mauldin III, R. L.; Berndt, T.; Sipilä, M.
  • Nature, Vol. 488, Issue 7410
  • DOI: 10.1038/nature11278

Cycloalkene Ozonolysis:  Collisionally Mediated Mechanistic Branching
journal, October 2004

  • Chuong, Bao; Zhang, Jieyuan; Donahue, Neil M.
  • Journal of the American Chemical Society, Vol. 126, Issue 39
  • DOI: 10.1021/ja0485412

Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor
journal, January 2015


Quantum chemical and RRKM/master equation studies of cyclopropene ozonolysis
journal, May 2011

  • Kuwata, Keith T.; Kujala, Brianna J.; Morrow, Zachary W.
  • Computational and Theoretical Chemistry, Vol. 965, Issue 2-3
  • DOI: 10.1016/j.comptc.2010.10.019

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


A kinetic study of the CH 2 OO Criegee intermediate self-reaction, reaction with SO 2 and unimolecular reaction using cavity ring-down spectroscopy
journal, January 2015

  • Chhantyal-Pun, Rabi; Davey, Anthony; Shallcross, Dudley E.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 5
  • DOI: 10.1039/C4CP04198D

Direct Observation of the Gas-Phase Criegee Intermediate (CH 2 OO)
journal, September 2008

  • Taatjes, Craig A.; Meloni, Giovanni; Selby, Talitha M.
  • Journal of the American Chemical Society, Vol. 130, Issue 36
  • DOI: 10.1021/ja804165q

Theoretical Investigation of Reaction Mechanisms for Carboxylic Acid Formation in the Atmosphere
journal, September 2000

  • Aplincourt, P.; Ruiz-López, M. F.
  • Journal of the American Chemical Society, Vol. 122, Issue 37
  • DOI: 10.1021/ja000731z

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

Secondary Organic Aerosol Formation from Aromatic Alkene Ozonolysis: Influence of the Precursor Structure on Yield, Chemical Composition, and Mechanism
journal, November 2018

  • Chiappini, Laura; Perraudin, Emilie; Maurin, Nicolas
  • The Journal of Physical Chemistry A, Vol. 123, Issue 7
  • DOI: 10.1021/acs.jpca.8b10394

Structure-dependent reactivity of Criegee intermediates studied with spectroscopic methods
journal, January 2017

  • Jr-Min Lin, Jim; Chao, Wen
  • Chemical Society Reviews, Vol. 46, Issue 24
  • DOI: 10.1039/C7CS00336F

Chemical Kinetics and Mechanisms of Complex Systems: A Perspective on Recent Theoretical Advances
journal, January 2014

  • Klippenstein, Stephen J.; Pande, Vijay S.; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 136, Issue 2
  • DOI: 10.1021/ja408723a

Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO 2 , H 2 O and decomposition under boundary layer conditions
journal, January 2015

  • Newland, Mike J.; Rickard, Andrew R.; Alam, Mohammed S.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 6
  • DOI: 10.1039/C4CP04186K

MESMER: An Open-Source Master Equation Solver for Multi-Energy Well Reactions
journal, September 2012

  • Glowacki, David R.; Liang, Chi-Hsiu; Morley, Christopher
  • The Journal of Physical Chemistry A, Vol. 116, Issue 38
  • DOI: 10.1021/jp3051033

Atmospheric photochemistry at a fatty acid-coated air-water interface
journal, August 2016


The gas-phase ozonolysis of β-caryophyllene (C15H24). Part II: A theoretical study
journal, January 2009

  • Nguyen, T. L.; Winterhalter, R.; Moortgat, G.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 21
  • DOI: 10.1039/b817913a

A modeling study of secondary organic aerosol formation from sesquiterpenes using the STOCHEM global chemistry and transport model: SOA FORMATION FROM SESQUITERPENES
journal, April 2017

  • Khan, M. A. H.; Jenkin, M. E.; Foulds, A.
  • Journal of Geophysical Research: Atmospheres, Vol. 122, Issue 8
  • DOI: 10.1002/2016JD026415

Criterion of minimum state density in the transition state theory of bimolecular reactions
journal, February 1979

  • Garrett, Bruce C.; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 70, Issue 4
  • DOI: 10.1063/1.437698

Theoretical kinetic study of the formic acid catalyzed Criegee intermediate isomerization: multistructural anharmonicity and atmospheric implications
journal, January 2018

  • Monge-Palacios, M.; Rissanen, Matti P.; Wang, Zhandong
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 16
  • DOI: 10.1039/C7CP08538A

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products
journal, November 2017

  • Green, Amy M.; Barber, Victoria P.; Fang, Yi
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 47
  • DOI: 10.1073/pnas.1715014114

Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications
journal, March 2014

  • Welz, Oliver; Eskola, Arkke J.; Sheps, Leonid
  • Angewandte Chemie International Edition, Vol. 53, Issue 18
  • DOI: 10.1002/anie.201400964

W2X and W3X-L: Cost-Effective Approximations to W2 and W4 with kJ mol –1 Accuracy
journal, April 2015


Extremely rapid self-reaction of the simplest Criegee intermediate CH2OO and its implications in atmospheric chemistry
journal, March 2014

  • Su, Yu-Te; Lin, Hui-Yu; Putikam, Raghunath
  • Nature Chemistry, Vol. 6, Issue 6
  • DOI: 10.1038/nchem.1890

Kinetics and Mechanisms of the Oxidation of Oxygenated Organic Compounds in the Gas Phase
journal, December 2003

  • Mellouki, A.; Le Bras, G.; Sidebottom, H.
  • Chemical Reviews, Vol. 103, Issue 12
  • DOI: 10.1021/cr020526x

Kinetics of the Strongly Correlated CH 3 O + O 2 Reaction: The Importance of Quadruple Excitations in Atmospheric and Combustion Chemistry
journal, November 2018

  • Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 141, Issue 1
  • DOI: 10.1021/jacs.8b11766

The 1,5-H-shift in 1-butoxy: A case study in the rigorous implementation of transition state theory for a multirotamer system
journal, September 2003

  • Vereecken, Luc; Peeters, Jozef
  • The Journal of Chemical Physics, Vol. 119, Issue 10
  • DOI: 10.1063/1.1597479

Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory
journal, March 2003

  • Lynch, Benjamin J.; Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 9
  • DOI: 10.1021/jp021590l

Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates
journal, July 2015

  • Lee, Yuan-Pern
  • The Journal of Chemical Physics, Vol. 143, Issue 2
  • DOI: 10.1063/1.4923165

Variational transition state theory: theoretical framework and recent developments
journal, January 2017

  • Bao, Junwei Lucas; Truhlar, Donald G.
  • Chemical Society Reviews, Vol. 46, Issue 24
  • DOI: 10.1039/C7CS00602K

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


Atmospheric Chemistry of Criegee Intermediates: Unimolecular Reactions and Reactions with Water
journal, October 2016

  • Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 138, Issue 43
  • DOI: 10.1021/jacs.6b08655

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

Insight into Chemistry on Cloud/Aerosol Water Surfaces
journal, April 2018


The Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of Cyclohexene
journal, October 2014

  • Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko
  • Journal of the American Chemical Society, Vol. 136, Issue 44
  • DOI: 10.1021/ja507146s

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


Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products
journal, September 2014


Theoretical studies of atmospheric reaction mechanisms in the troposphere
journal, January 2012

  • Vereecken, Luc; Francisco, Joseph S.
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35070j

Infrared Absorption Spectrum of the Simplest Criegee Intermediate CH2OO
journal, April 2013


Quantum chemical and RRKM/master equation studies of isoprene ozonolysis: Methacrolein and methacrolein oxide
journal, January 2008


Unimolecular reaction of acetone oxide and its reaction with water in the atmosphere
journal, May 2018

  • Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 24
  • DOI: 10.1073/pnas.1804453115

Kinetics of the unimolecular reaction of CH 2 OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditions
journal, January 2015

  • Berndt, Torsten; Kaethner, Ralf; Voigtländer, Jens
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 30
  • DOI: 10.1039/C5CP02224J

Implications of ω-oxocarboxylic acids in the remote marine atmosphere for photo-oxidation of unsaturated fatty acids
journal, January 1987

  • Kawamura, K.; Gagosian, R. B.
  • Nature, Vol. 325, Issue 6102
  • DOI: 10.1038/325330a0

    Works referencing / citing this record: