skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Deep tunneling in the unimolecular decay of CH 3CHOO Criegee intermediates to OH radical products

Abstract

Unimolecular decay of Criegee intermediates produced in alkene ozonolysis is known to be a significant source of OH radicals in the troposphere. In this work, unimolecular decay of the methyl-substituted Criegee intermediate, syn-CH 3CHOO, to OH products is shown to occur at energies significantly below the transition state barrier for a 1,4 hydrogen transfer that leads to these products [Y. Fang et al., J. Chem. Phys. 144, 061102 (2016)]. The rate of appearance of OH products arising from tunneling through the barrier is obtained through direct time-domain measurements following the vibrational activation of syn-CH 3CHOO. IR excitation of syn-CH 3CHOO at energies nearly 2000 cm -1 below the barrier is achieved through combination bands involving CH stretch and another lower frequency mode, and the resultant OH products are detected by UV laser-induced fluorescence. The observed syn-CH 3CHOO combination bands in the 4100–4350 cm -1 region are identified by comparison with the computed IR absorption spectrum. The experimental decay rates are found to be ca. 106 s -1 in this deep tunneling regime, which is approximately 100-times slower than that in the vicinity of the barrier.The experimental results are consistent with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical decay rates withmore » tunneling through the barrier, and notable deviations may originate from the sparsity in the density of states for syn-CH 3CHOO at lower energies. Thermal unimolecular decay of syn-CH 3CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.« less

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [1]
  1. Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA
  2. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA
  3. Department of Chemistry, University of Washington, Seattle, Washington 98195, USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1373744
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 23; 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; ab initio kinetics; creigee intermediate; tunneling; unimolecular decay

Citation Formats

Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products. United States: N. p., 2016. Web. doi:10.1063/1.4972015.
Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., & Lester, Marsha I. Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products. United States. doi:10.1063/1.4972015.
Fang, Yi, Liu, Fang, Barber, Victoria P., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Mon . "Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products". United States. doi:10.1063/1.4972015.
@article{osti_1373744,
title = {Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products},
author = {Fang, Yi and Liu, Fang and Barber, Victoria P. and Klippenstein, Stephen J. and McCoy, Anne B. and Lester, Marsha I.},
abstractNote = {Unimolecular decay of Criegee intermediates produced in alkene ozonolysis is known to be a significant source of OH radicals in the troposphere. In this work, unimolecular decay of the methyl-substituted Criegee intermediate, syn-CH3CHOO, to OH products is shown to occur at energies significantly below the transition state barrier for a 1,4 hydrogen transfer that leads to these products [Y. Fang et al., J. Chem. Phys. 144, 061102 (2016)]. The rate of appearance of OH products arising from tunneling through the barrier is obtained through direct time-domain measurements following the vibrational activation of syn-CH3CHOO. IR excitation of syn-CH3CHOO at energies nearly 2000 cm-1 below the barrier is achieved through combination bands involving CH stretch and another lower frequency mode, and the resultant OH products are detected by UV laser-induced fluorescence. The observed syn-CH3CHOO combination bands in the 4100–4350 cm-1 region are identified by comparison with the computed IR absorption spectrum. The experimental decay rates are found to be ca. 106 s-1 in this deep tunneling regime, which is approximately 100-times slower than that in the vicinity of the barrier.The experimental results are consistent with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical decay rates with tunneling through the barrier, and notable deviations may originate from the sparsity in the density of states for syn-CH3CHOO at lower energies. Thermal unimolecular decay of syn-CH3CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.},
doi = {10.1063/1.4972015},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 23,
volume = 145,
place = {United States},
year = {2016},
month = {12}
}

Works referenced in this record:

Improved Multidimensional Semiclassical Tunneling Theory
journal, November 2013

  • Wagner, Albert F.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 49
  • DOI: 10.1021/jp409720s

Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene
journal, January 2016

  • Nguyen, Tran B.; Tyndall, Geoffrey S.; Crounse, John D.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 15
  • DOI: 10.1039/C6CP00053C

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

Known and Unexplored Organic Constituents in the Earth's Atmosphere
journal, March 2007

  • Goldstein, Allen H.; Galbally, Ian E.
  • Environmental Science & Technology, Vol. 41, Issue 5
  • DOI: 10.1021/es072476p

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

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

Connecting Chemical Dynamics in Gases and Liquids
journal, May 2006


Fourier-transform microwave spectroscopy of an alkyl substituted Criegee intermediate anti-CH3CHOO
journal, April 2015


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

Total radical yields from tropospheric ethene ozonolysis
journal, January 2011

  • Alam, Mohammed S.; Camredon, Marie; Rickard, Andrew R.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 23
  • DOI: 10.1039/c0cp02342f

A transition state theory‐based statistical distribution of unimolecular decay rates with application to unimolecular decomposition of formaldehyde
journal, October 1990

  • Miller, William H.; Hernandez, Rigoberto; Moore, C. Bradley
  • The Journal of Chemical Physics, Vol. 93, Issue 8
  • DOI: 10.1063/1.459636

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

Kinetic and Theoretical Investigation of the Gas-Phase Ozonolysis of Isoprene:  Carbonyl Oxides as an Important Source for OH Radicals in the Atmosphere
journal, August 1997

  • Gutbrod, Roland; Kraka, Elfi; Schindler, Ralph N.
  • Journal of the American Chemical Society, Vol. 119, Issue 31
  • DOI: 10.1021/ja970050c

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


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

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

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states
journal, March 2015

  • Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.
  • The Journal of Chemical Physics, Vol. 142, Issue 12
  • DOI: 10.1063/1.4914987

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

Direct Kinetic Measurements of Criegee Intermediate (CH2OO) Formed by Reaction of CH2I with O2
journal, January 2012


The addition and dissociation reaction atomic hydrogen + carbon monoxide .dblharw. oxomethyl. 1. Theoretical RRKM studies
journal, September 1987

  • Wagner, Albert F.; Bowman, Joel M.
  • The Journal of Physical Chemistry, Vol. 91, Issue 20
  • DOI: 10.1021/j100304a036

Impact of the water dimer on the atmospheric reactivity of carbonyl oxides
journal, January 2016

  • Anglada, Josep M.; Solé, Albert
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 26
  • DOI: 10.1039/C6CP02531E

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


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

Theoretical/experimental comparison of deep tunneling decay of quasi-bound H(D)OCO to H(D) + CO 2
journal, August 2014

  • Wagner, Albert F.; Dawes, Richard; Continetti, Robert E.
  • The Journal of Chemical Physics, Vol. 141, Issue 5
  • DOI: 10.1063/1.4891675

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

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

Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation
journal, January 2013

  • Percival, Carl J.; Welz, Oliver; Eskola, Arkke J.
  • Faraday Discussions, Vol. 165
  • DOI: 10.1039/c3fd00048f

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

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH, HO2 and RO2
journal, October 2005

  • Emmerson, K. M.; Carslaw, N.; Pilling, M. J.
  • Journal of Atmospheric Chemistry, Vol. 52, Issue 2
  • DOI: 10.1007/s10874-005-1323-2

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

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

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


Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn -CH 3 CHOO through pure rotational transitions
journal, January 2014

  • Nakajima, Masakazu; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 140, Issue 1
  • DOI: 10.1063/1.4861494

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

Temperature dependence of the reaction of anti-CH 3 CHOO with water vapor
journal, January 2016

  • Lin, Liang-Chun; Chao, Wen; Chang, Chun-Hung
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 40
  • DOI: 10.1039/C6CP05171E

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

UV absorption probing of the conformer-dependent reactivity of a Criegee intermediate CH 3 CHOO
journal, January 2014

  • Sheps, Leonid; Scully, Ashley M.; Au, Kendrew
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 48
  • DOI: 10.1039/C4CP04408H

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


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

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


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

Direct evidence for a substantive reaction between the Criegee intermediate, CH 2 OO, and the water vapour dimer
journal, January 2015

  • Lewis, Tom R.; Blitz, Mark A.; Heard, Dwayne E.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 7
  • DOI: 10.1039/C4CP04750H

Harmonic and Anharmonic Vibrational Frequency Calculations with the Double-Hybrid B2PLYP Method: Analytic Second Derivatives and Benchmark Studies
journal, June 2010

  • Biczysko, Malgorzata; Panek, Pawel; Scalmani, Giovanni
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 7
  • DOI: 10.1021/ct100212p

DSD-BLYP: A General Purpose Double Hybrid Density Functional Including Spin Component Scaling and Dispersion Correction
journal, October 2010

  • Kozuch, Sebastian; Gruzman, David; Martin, Jan M. L.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 48
  • DOI: 10.1021/jp1070852

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

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

Communication: New insight into the barrier governing CO2 formation from OH + CO
journal, May 2011

  • Johnson, Christopher J.; Poad, Berwyck L. J.; Shen, Ben B.
  • The Journal of Chemical Physics, Vol. 134, Issue 17
  • DOI: 10.1063/1.3589860