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Relatively Selective Production of the Simplest Criegee Intermediate in a CH4/O2 Electric Discharge: Kinetic Analysis of a Plausible Mechanism

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† Department of Chemistry, The University of Texas at Austin, Mail Stop A5300, Austin, Texas 78712-0165, United States
‡ Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138, United States
*E-mail: [email protected]
Cite this: J. Phys. Chem. A 2015, 119, 28, 7197–7204
Publication Date (Web):November 18, 2014
https://doi.org/10.1021/jp510554g
Copyright © 2014 American Chemical Society
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Abstract

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High -accuracy coupled cluster methods in combination with microcanonical semiclassical transition state theory are used to investigate a plausible formation mechanism of the simplest Criegee intermediate in a CH4/O2 discharge experiment. Our results suggest that the Criegee intermediate is produced in a three-step process: (i) production of methyl radical by cleavage of a C–H bond of CH4; (ii) association of methyl radical with molecular oxygen to form a vibrationally excited methyl peroxy, which is in a rapid microequilibrium with the reactants; and finally, (iii) H-abstraction of CH3OO by O2, which results in the formation of cool CH2OO, which has insufficient internal energy to rearrange to dioxirane.

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Optimized geometries, rovibrational parameters, anharmonic constants, thermal rate constants, and energies for various species in the reaction of 2O2 with CH3/CD3 are given. In addition, the reaction mechanisms of H + CH3OO and HO + CH3OO are presented. This material is available free of charge via the Internet at http://pubs.acs.org.

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Cited By

This article is cited by 16 publications.

  1. Vincent J. Esposito, Tianlin Liu, Guanghan Wang, Adriana Caracciolo, Michael F. Vansco, Barbara Marchetti, Tolga N. V. Karsili, Marsha I. Lester. Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory. The Journal of Physical Chemistry A 2021, 125 (30) , 6571-6579. https://doi.org/10.1021/acs.jpca.1c03643
  2. Bradley K. Welch, Richard Dawes, David H. Bross, Branko Ruscic. An Automated Thermochemistry Protocol Based on Explicitly Correlated Coupled-Cluster Theory: The Methyl and Ethyl Peroxy Families. The Journal of Physical Chemistry A 2019, 123 (26) , 5673-5682. https://doi.org/10.1021/acs.jpca.9b04381
  3. Aaron M. Thomas, Beni B. Dangi, Tao Yang, György Tarczay, Ralf I. Kaiser, , Bing-Jian Sun, Si-Ying Chen, Agnes H. H. Chang, , Thanh L. Nguyen, John F. Stanton, , Alexander M. Mebel. Directed Gas-Phase Formation of the Germaniumsilylene Butterfly Molecule (Ge(μ-H2)Si). The Journal of Physical Chemistry Letters 2019, 10 (6) , 1264-1271. https://doi.org/10.1021/acs.jpclett.9b00284
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  5. Jessica P. Porterfield, Thanh Lam Nguyen, Joshua H. Baraban, Grant T. Buckingham, Tyler P. Troy, Oleg Kostko, Musahid Ahmed, John F. Stanton, John W. Daily, and G. Barney Ellison . Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor. The Journal of Physical Chemistry A 2015, 119 (51) , 12635-12647. https://doi.org/10.1021/acs.jpca.5b10984
  6. Luc Vereecken, David R. Glowacki, and Michael J. Pilling . Theoretical Chemical Kinetics in Tropospheric Chemistry: Methodologies and Applications. Chemical Reviews 2015, 115 (10) , 4063-4114. https://doi.org/10.1021/cr500488p
  7. Justin P. Wiens, Nicholas S. Shuman, and Albert A. Viggiano . Production of and Dissociative Electron Attachment to the Simplest Criegee Intermediate in an Afterglow. The Journal of Physical Chemistry Letters 2015, 6 (3) , 383-387. https://doi.org/10.1021/jz502569w
  8. Tolga N. V. Karsili, Barbara Marchetti, Marsha I. Lester, Michael N. R. Ashfold. Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates. Photochemistry and Photobiology 2023, 99 (1) , 4-18. https://doi.org/10.1111/php.13665
  9. Thanh Lam Nguyen, A.R. Ravishankara, John F. Stanton. Analysis of the potential atmospheric impact of the reaction of N2O with OH. Chemical Physics Letters 2018, 708 , 100-105. https://doi.org/10.1016/j.cplett.2018.08.014
  10. M. A. H. Khan, C. J. Percival, R. L. Caravan, C. A. Taatjes, D. E. Shallcross. Criegee intermediates and their impacts on the troposphere. Environmental Science: Processes & Impacts 2018, 20 (3) , 437-453. https://doi.org/10.1039/C7EM00585G
  11. Michael C. McCarthy, Kin Long Kelvin Lee, John F. Stanton. Detection and structural characterization of nitrosamide H 2 NNO: A central intermediate in deNO x processes. The Journal of Chemical Physics 2017, 147 (13) , 134301. https://doi.org/10.1063/1.4992097
  12. Yanli Liu, Long Chen, Dongping Chen, Weina Wang, Fengyi Liu, Wenliang Wang. Computational study on mechanisms of C2H5O2+OH reaction and properties of C2H5O3H complex. Chemical Research in Chinese Universities 2017, 33 (4) , 623-630. https://doi.org/10.1007/s40242-017-7055-4
  13. Michael F. Vansco, Hongwei Li, Marsha I. Lester. Prompt release of O 1 D products upon UV excitation of CH 2 OO Criegee intermediates. The Journal of Chemical Physics 2017, 147 (1) , 013907. https://doi.org/10.1063/1.4977987
  14. Jean-François Müller, Zhen Liu, Vinh Son Nguyen, Trissevgeni Stavrakou, Jeremy N. Harvey, Jozef Peeters. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol. Nature Communications 2016, 7 (1) https://doi.org/10.1038/ncomms13213
  15. Yuan-Pern Lee. Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates. The Journal of Chemical Physics 2015, 143 (2) , 020901. https://doi.org/10.1063/1.4923165
  16. Caroline C. Womack, Marie-Aline Martin-Drumel, Gordon G. Brown, Robert W. Field, Michael C. McCarthy. Observation of the simplest Criegee intermediate CH 2 OO in the gas-phase ozonolysis of ethylene. Science Advances 2015, 1 (2) , e1400105. https://doi.org/10.1126/sciadv.1400105

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