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Title: Tunneling effects in the unimolecular decay of (CH 3) 2COO Criegee intermediates to OH radical products

Abstract

Unimolecular decay of the dimethyl substituted Criegee intermediate (CH 3) 2COO is observed at energies significantly below the transition state barrier associated with hydrogen atom transfer with time-resolved detection of the resultant OH radical products. (CH 3) 2COO is prepared at specific energies in the 3900-4600 cm -1 region through IR excitation of combination bands involving CH stretch and another lower frequency mode, and the OH products are detected by UV laser-induced fluorescence. OH appearance times on the order of microseconds are observed in this deep tunneling regime, which are about 100 times slower than that in the vicinity of the barrier. The experimental rates are in good accord with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical dissociation rates for (CH 3) 2COO that include tunneling. Master equation modeling based on these microcanonical rates is used to predict the thermal decay rate of (CH 3) 2COO to OH products under atmospheric conditions of 276 s -1 at 298 K (high pressure limit). Furthermore, thermal unimolecular decay of (CH 3) 2COO to OH products is shown to have significant contributions from tunneling at energies much below the barrier to H-atom transfer.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division; USDOE
OSTI Identifier:
1371548
Alternate Identifier(s):
OSTI ID: 1361798
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fang, Yi, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products. United States: N. p., 2017. Web. doi:10.1063/1.4979297.
Fang, Yi, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., & Lester, Marsha I. Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products. United States. doi:10.1063/1.4979297.
Fang, Yi, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Tue . "Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products". United States. doi:10.1063/1.4979297. https://www.osti.gov/servlets/purl/1371548.
@article{osti_1371548,
title = {Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products},
author = {Fang, Yi and Barber, Victoria P. and Klippenstein, Stephen J. and McCoy, Anne B. and Lester, Marsha I.},
abstractNote = {Unimolecular decay of the dimethyl substituted Criegee intermediate (CH3)2COO is observed at energies significantly below the transition state barrier associated with hydrogen atom transfer with time-resolved detection of the resultant OH radical products. (CH3)2COO is prepared at specific energies in the 3900-4600 cm-1 region through IR excitation of combination bands involving CH stretch and another lower frequency mode, and the OH products are detected by UV laser-induced fluorescence. OH appearance times on the order of microseconds are observed in this deep tunneling regime, which are about 100 times slower than that in the vicinity of the barrier. The experimental rates are in good accord with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical dissociation rates for (CH3)2COO that include tunneling. Master equation modeling based on these microcanonical rates is used to predict the thermal decay rate of (CH3)2COO to OH products under atmospheric conditions of 276 s-1 at 298 K (high pressure limit). Furthermore, thermal unimolecular decay of (CH3)2COO to OH products is shown to have significant contributions from tunneling at energies much below the barrier to H-atom transfer.},
doi = {10.1063/1.4979297},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 146,
place = {United States},
year = {2017},
month = {4}
}

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Cited by: 8 works
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Works referenced in this record:

Fourier-transform microwave spectroscopy of dimethyl-substituted Criegee intermediate (CH 3 ) 2 COO
journal, December 2016

  • Nakajima, Masakazu; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 145, Issue 24
  • DOI: 10.1063/1.4973014

Tunnelling Corrections for Unsymmetrical Eckart Potential Energy Barriers
journal, March 1962

  • Johnston, Harold S.; Heicklen, Julian
  • The Journal of Physical Chemistry, Vol. 66, Issue 3
  • DOI: 10.1021/j100809a040

Velocity map imaging of OH radical products from IR activated (CH3)2COO Criegee intermediates
journal, September 2016

  • Li, Hongwei; Kidwell, Nathanael M.; Wang, Xiaohong
  • The Journal of Chemical Physics, Vol. 145, Issue 10
  • DOI: 10.1063/1.4962361

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

Unimolecular Isomerizations and Oxygen Atom Loss in Formaldehyde and Acetaldehyde Carbonyl Oxides. A Theoretical Investigation
journal, January 1996

  • Anglada, Josep M.; Bofill, Josep M.; Olivella, Santiago
  • Journal of the American Chemical Society, Vol. 118, Issue 19
  • DOI: 10.1021/ja953858a

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

Energetics, Kinetics, and Product Distributions of the Reactions of Ozone with Ethene and 2,3-Dimethyl-2-butene
journal, December 1997

  • Olzmann, M.; Kraka, E.; Cremer, D.
  • The Journal of Physical Chemistry A, Vol. 101, Issue 49
  • DOI: 10.1021/jp971663e

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

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


Stabilization of the Simplest Criegee Intermediate from the Reaction between Ozone and Ethylene: A High-Level Quantum Chemical and Kinetic Analysis of Ozonolysis
journal, May 2015

  • Nguyen, Thanh Lam; Lee, Hyunwoo; Matthews, Devin A.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 22
  • DOI: 10.1021/acs.jpca.5b02088

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

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

Deep tunneling in the unimolecular decay of CH 3 CHOO Criegee intermediates to OH radical products
journal, December 2016

  • Fang, Yi; Liu, Fang; Barber, Victoria P.
  • The Journal of Chemical Physics, Vol. 145, Issue 23
  • DOI: 10.1063/1.4972015

A Convenient Synthesis of Ethylidine Iodide
journal, January 1975

  • Friedrich, Edwin C.; Falling, Stephen N.; Lyons, David E.
  • Synthetic Communications, Vol. 5, Issue 1
  • DOI: 10.1080/00397917508063512

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

Communication: Thermal unimolecular decomposition of syn-CH 3 CHOO: A kinetic study
journal, October 2016

  • Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C.
  • The Journal of Chemical Physics, Vol. 145, Issue 13
  • DOI: 10.1063/1.4964393

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

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO 2
journal, August 2015

  • Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 35
  • DOI: 10.1073/pnas.1513149112

Unimolecular Decomposition Rate of the Criegee Intermediate (CH 3 ) 2 COO Measured Directly with UV Absorption Spectroscopy
journal, February 2016

  • Smith, Mica C.; Chao, Wen; Takahashi, Kaito
  • The Journal of Physical Chemistry A, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpca.5b12124

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

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


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

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

Direct observation of unimolecular decay of CH 3 CH 2 CHOO Criegee intermediates to OH radical products
journal, July 2016

  • Fang, Yi; Liu, Fang; Klippenstein, Stephen J.
  • The Journal of Chemical Physics, Vol. 145, Issue 4
  • DOI: 10.1063/1.4958992

Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products
journal, February 2016

  • Fang, Yi; Liu, Fang; Barber, Victoria P.
  • The Journal of Chemical Physics, Vol. 144, Issue 6
  • DOI: 10.1063/1.4941768

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

Direct production of OH radicals upon CH overtone activation of (CH 3 ) 2 COO Criegee intermediates
journal, December 2014

  • Liu, Fang; Beames, Joseph M.; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 141, Issue 23
  • DOI: 10.1063/1.4903961

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

    Works referencing / citing this record:

    Temperature and isotope effects in the reaction of CH 3 CHOO with methanol
    journal, January 2019

    • Chao, Wen; Lin, Yen-Hsiu; Yin, Cangtao
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 25
    • DOI: 10.1039/c9cp02534k

    Temperature and isotope effects in the reaction of CH 3 CHOO with methanol
    journal, January 2019

    • Chao, Wen; Lin, Yen-Hsiu; Yin, Cangtao
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 25
    • DOI: 10.1039/c9cp02534k