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

Abstract

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Furthermore, complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 107 s-1, which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s-1 at 298 K.

Authors:
 [1]; ORCiD logo [1];  [2];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1350088
Alternate Identifier(s):
OSTI ID: 1273668
Grant/Contract Number:  
AC02-06CH11357; CHE-1362835
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 4; 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; RRKM theory; creigee intermediate; photodissociation

Citation Formats

Fang, Yi, Liu, Fang, Klippenstein, Stephen J., and Lester, Marsha I. Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products. United States: N. p., 2016. Web. doi:10.1063/1.4958992.
Fang, Yi, Liu, Fang, Klippenstein, Stephen J., & Lester, Marsha I. Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products. United States. doi:10.1063/1.4958992.
Fang, Yi, Liu, Fang, Klippenstein, Stephen J., and Lester, Marsha I. Wed . "Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products". United States. doi:10.1063/1.4958992. https://www.osti.gov/servlets/purl/1350088.
@article{osti_1350088,
title = {Direct observation of unimolecular decay of CH3CH2CHOO Criegee intermediates to OH radical products},
author = {Fang, Yi and Liu, Fang and Klippenstein, Stephen J. and Lester, Marsha I.},
abstractNote = {The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Furthermore, complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 107 s-1, which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s-1 at 298 K.},
doi = {10.1063/1.4958992},
journal = {Journal of Chemical Physics},
number = 4,
volume = 145,
place = {United States},
year = {2016},
month = {7}
}

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Works referenced in this record:

Simplified CCSD(T)-F12 methods: Theory and benchmarks
journal, February 2009

  • Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 130, Issue 5
  • DOI: 10.1063/1.3054300

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


The reactions of ozone with alkenes: An important source of HO x in the boundary layer
journal, December 1996

  • Paulson, Suzanne E.; Orlando, John J.
  • Geophysical Research Letters, Vol. 23, Issue 25
  • DOI: 10.1029/96GL03477

Tropospheric OH and HO2 radicals: field measurements and model comparisons
journal, January 2012

  • Stone, Daniel; Whalley, Lisa K.; Heard, Dwayne E.
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35140d

Direct observation of OH formation from stabilised Criegee intermediates
journal, January 2014

  • Novelli, A.; Vereecken, L.; Lelieveld, J.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 37
  • DOI: 10.1039/C4CP02719A

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

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

Night-time radical chemistry during the TORCH campaign
journal, June 2009


Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar
journal, February 2008

  • Peterson, Kirk A.; Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 128, Issue 8
  • DOI: 10.1063/1.2831537

Semiclassical limit of quantum mechanical transition state theory for nonseparable systems
journal, March 1975

  • Miller, William H.
  • The Journal of Chemical Physics, Vol. 62, Issue 5
  • DOI: 10.1063/1.430676

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

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


Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon
journal, September 1995

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 103, Issue 11
  • DOI: 10.1063/1.470645

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

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

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

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

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

UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH 3 CHOO
journal, June 2013

  • Beames, Joseph M.; Liu, Fang; Lu, Lu
  • The Journal of Chemical Physics, Vol. 138, Issue 24
  • DOI: 10.1063/1.4810865

Free radical modelling studies during the UK TORCH Campaign in Summer 2003
journal, January 2007

  • Emmerson, K. M.; Carslaw, N.; Carslaw, D. C.
  • Atmospheric Chemistry and Physics, Vol. 7, Issue 1
  • DOI: 10.5194/acp-7-167-2007

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

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

A practical implementation of semi-classical transition state theory for polyatomics
journal, October 2010


    Works referencing / citing this record:

    Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes
    journal, January 2018

    • Rickly, Pamela; Stevens, Philip S.
    • Atmospheric Measurement Techniques, Vol. 11, Issue 1
    • DOI: 10.5194/amt-11-1-2018

    Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes
    journal, January 2018

    • Rickly, Pamela; Stevens, Philip S.
    • Atmospheric Measurement Techniques, Vol. 11, Issue 1
    • DOI: 10.5194/amt-11-1-2018