Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products

Fang, Yi; Barber, Victoria P.; Klippenstein, Stephen J.; McCoy, Anne B.; Lester, Marsha I.

doi:10.1063/1.4979297

Title: Tunneling effects in the unimolecular decay of (CH₃)₂COO Criegee intermediates to OH radical products

Journal Article · Tue Apr 04 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4979297· OSTI ID:1371548

^[1]; Barber, Victoria P. ^[1];

^[2];

^[3];

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Washington, Seattle, WA (United States)

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.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division; USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1371548

Alternate ID(s):: OSTI ID: 1361798

Journal Information:: Journal of Chemical Physics, Vol. 146, Issue 13; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 29 works

Citation information provided by
Web of Science

References (34)

Fourier-transform microwave spectroscopy of dimethyl-substituted Criegee intermediate (CH ₃ ) ₂ COO Nakajima, Masakazu; Endo, Yasuki The Journal of Chemical Physics, Vol. 145, Issue 24 https://doi.org/10.1063/1.4973014	journal	December 2016
Tunnelling Corrections for Unsymmetrical Eckart Potential Energy Barriers Johnston, Harold S.; Heicklen, Julian The Journal of Physical Chemistry, Vol. 66, Issue 3 https://doi.org/10.1021/j100809a040	journal	March 1962
Velocity map imaging of OH radical products from IR activated (CH3)2COO Criegee intermediates Li, Hongwei; Kidwell, Nathanael M.; Wang, Xiaohong The Journal of Chemical Physics, Vol. 145, Issue 10 https://doi.org/10.1063/1.4962361	journal	September 2016
Direct evidence for a substantive reaction between the Criegee intermediate, CH ₂ OO, and the water vapour dimer Lewis, Tom R.; Blitz, Mark A.; Heard, Dwayne E. Physical Chemistry Chemical Physics, Vol. 17, Issue 7 https://doi.org/10.1039/c4cp04750h	journal	January 2015
UV Spectroscopic Characterization of Dimethyl- and Ethyl-Substituted Carbonyl Oxides Liu, Fang; Beames, Joseph M.; Green, Amy M. The Journal of Physical Chemistry A, Vol. 118, Issue 12 https://doi.org/10.1021/jp412726z	journal	March 2014
Temperature dependence of the reaction of anti-CH ₃ CHOO with water vapor Lin, Liang-Chun; Chao, Wen; Chang, Chun-Hung Physical Chemistry Chemical Physics, Vol. 18, Issue 40 https://doi.org/10.1039/c6cp05171e	journal	January 2016
A kinetic study of the CH ₂ OO Criegee intermediate self-reaction, reaction with SO ₂ and unimolecular reaction using cavity ring-down spectroscopy Chhantyal-Pun, Rabi; Davey, Anthony; Shallcross, Dudley E. Physical Chemistry Chemical Physics, Vol. 17, Issue 5 https://doi.org/10.1039/c4cp04198d	journal	January 2015
Kinetics of the unimolecular reaction of CH ₂ OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditions Berndt, Torsten; Kaethner, Ralf; Voigtländer, Jens Physical Chemistry Chemical Physics, Vol. 17, Issue 30 https://doi.org/10.1039/c5cp02224j	journal	January 2015
Unimolecular Isomerizations and Oxygen Atom Loss in Formaldehyde and Acetaldehyde Carbonyl Oxides. A Theoretical Investigation Anglada, Josep M.; Bofill, Josep M.; Olivella, Santiago Journal of the American Chemical Society, Vol. 118, Issue 19 https://doi.org/10.1021/ja953858a	journal	January 1996
Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products Kidwell, Nathanael M.; Li, Hongwei; Wang, Xiaohong Nature Chemistry, Vol. 8, Issue 5 https://doi.org/10.1038/nchem.2488	journal	April 2016
Production of OH radicals from the reactions of C4–C6 internal alkenes and styrenes with ozone in the gas phase Orzechowska, Grazyna E.; Paulson, Suzanne E. Atmospheric Environment, Vol. 36, Issue 3 https://doi.org/10.1016/s1352-2310(01)00445-9	journal	January 2002
Energetics, Kinetics, and Product Distributions of the Reactions of Ozone with Ethene and 2,3-Dimethyl-2-butene Olzmann, M.; Kraka, E.; Cremer, D. The Journal of Physical Chemistry A, Vol. 101, Issue 49 https://doi.org/10.1021/jp971663e	journal	December 1997
Computational Studies of the Isomerization and Hydration Reactions of Acetaldehyde Oxide and Methyl Vinyl Carbonyl Oxide Kuwata, Keith T.; Hermes, Matthew R.; Carlson, Matthew J. The Journal of Physical Chemistry A, Vol. 114, Issue 34 https://doi.org/10.1021/jp105358v	journal	September 2010
Semiclassical transition state theory. A new perspective Hernandez, Rigoberto; Miller, William H. Chemical Physics Letters, Vol. 214, Issue 2 https://doi.org/10.1016/0009-2614(93)90071-8	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 Nguyen, Thanh Lam; Lee, Hyunwoo; Matthews, Devin A. The Journal of Physical Chemistry A, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpca.5b02088	journal	May 2015
Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates Lee, Yuan-Pern The Journal of Chemical Physics, Vol. 143, Issue 2 https://doi.org/10.1063/1.4923165	journal	July 2015
Adventures in ozoneland: down the rabbit-hole Donahue, Neil M.; Drozd, Greg T.; Epstein, Scott A. Physical Chemistry Chemical Physics, Vol. 13, Issue 23 https://doi.org/10.1039/c0cp02564j	journal	January 2011
Deep tunneling in the unimolecular decay of CH ₃ CHOO Criegee intermediates to OH radical products Fang, Yi; Liu, Fang; Barber, Victoria P. The Journal of Chemical Physics, Vol. 145, Issue 23 https://doi.org/10.1063/1.4972015	journal	December 2016
A Convenient Synthesis of Ethylidine Iodide Friedrich, Edwin C.; Falling, Stephen N.; Lyons, David E. Synthetic Communications, Vol. 5, Issue 1 https://doi.org/10.1080/00397917508063512	journal	January 1975
Mechanism of HO _x Formation in the Gas-Phase Ozone-Alkene Reaction. 2. Prompt versus Thermal Dissociation of Carbonyl Oxides to Form OH Kroll, Jesse H.; Sahay, Shailesh R.; Anderson, James G. The Journal of Physical Chemistry A, Vol. 105, Issue 18 https://doi.org/10.1021/jp004136v	journal	May 2001
Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation Percival, Carl J.; Welz, Oliver; Eskola, Arkke J. Faraday Discussions, Vol. 165 https://doi.org/10.1039/C3FD00048F	journal	January 2013
Communication: Thermal unimolecular decomposition of syn-CH ₃ CHOO: A kinetic study Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C. The Journal of Chemical Physics, Vol. 145, Issue 13 https://doi.org/10.1063/1.4964393	journal	October 2016
Atmospheric Chemistry of Criegee Intermediates: Unimolecular Reactions and Reactions with Water Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G. Journal of the American Chemical Society, Vol. 138, Issue 43 https://doi.org/10.1021/jacs.6b08655	journal	October 2016
Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂ Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min Proceedings of the National Academy of Sciences, Vol. 112, Issue 35 https://doi.org/10.1073/pnas.1513149112	journal	August 2015
Unimolecular Decomposition Rate of the Criegee Intermediate (CH ₃ ) ₂ COO Measured Directly with UV Absorption Spectroscopy Smith, Mica C.; Chao, Wen; Takahashi, Kaito The Journal of Physical Chemistry A, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpca.5b12124	journal	February 2016
A new atmospherically relevant oxidant of sulphur dioxide Mauldin III, R. L.; Berndt, T.; Sipilä, M. Nature, Vol. 488, Issue 7410 https://doi.org/10.1038/nature11278	journal	August 2012
Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor Chao, W.; Hsieh, J. -T.; Chang, C. -H. Science, Vol. 347, Issue 6223 https://doi.org/10.1126/science.1261549	journal	January 2015
Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH ₃ ) ₂ COO Chhantyal-Pun, Rabi; Welz, Oliver; Savee, John D. The Journal of Physical Chemistry A, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpca.6b07810	journal	December 2016
Theoretical studies of atmospheric reaction mechanisms in the troposphere Vereecken, Luc; Francisco, Joseph S. Chemical Society Reviews, Vol. 41, Issue 19 https://doi.org/10.1039/c2cs35070j	journal	January 2012
Direct observation of unimolecular decay of CH ₃ CH ₂ CHOO Criegee intermediates to OH radical products Fang, Yi; Liu, Fang; Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 145, Issue 4 https://doi.org/10.1063/1.4958992	journal	July 2016
Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products Fang, Yi; Liu, Fang; Barber, Victoria P. The Journal of Chemical Physics, Vol. 144, Issue 6 https://doi.org/10.1063/1.4941768	journal	February 2016
The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere Johnson, David; Marston, George Chemical Society Reviews, Vol. 37, Issue 4 https://doi.org/10.1039/b704260b	journal	January 2008
Direct production of OH radicals upon CH overtone activation of (CH ₃ ) ₂ COO Criegee intermediates Liu, Fang; Beames, Joseph M.; Lester, Marsha I. The Journal of Chemical Physics, Vol. 141, Issue 23 https://doi.org/10.1063/1.4903961	journal	December 2014
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010

Cited By (6)

Effect of unsaturated substituents in the reaction of Criegee intermediates with water vapor Yin, Cangtao; Takahashi, Kaito Physical Chemistry Chemical Physics, Vol. 20, Issue 30 https://doi.org/10.1039/c8cp02064g	journal	January 2018
Temperature and isotope effects in the reaction of CH 3 CHOO with methanol Chao, Wen; Lin, Yen-Hsiu; Yin, Cangtao Physical Chemistry Chemical Physics, Vol. 21, Issue 25 https://doi.org/10.1039/c9cp02534k	journal	January 2019
Conformational preferences of Criegee intermediates: Isopropyl substituted carbonyl oxide Cabezas, Carlos; Guillemin, Jean-Claude; Endo, Yasuki The Journal of Chemical Physics, Vol. 149, Issue 8 https://doi.org/10.1063/1.5045768	journal	August 2018
Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis Vansco, Michael F.; Marchetti, Barbara; Lester, Marsha I. The Journal of Chemical Physics, Vol. 149, Issue 24 https://doi.org/10.1063/1.5064716	journal	December 2018
Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products Green, Amy M.; Barber, Victoria P.; Fang, Yi Proceedings of the National Academy of Sciences, Vol. 114, Issue 47 https://doi.org/10.1073/pnas.1715014114	journal	November 2017
Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact Stephenson, Thomas A.; Lester, Marsha I. International Reviews in Physical Chemistry, Vol. 39, Issue 1 https://doi.org/10.1080/0144235x.2020.1688530	journal	December 2019

Similar Records

Deep tunneling in the unimolecular decay of CH₃CHOO Criegee intermediates to OH radical products

Journal Article · Mon Dec 19 00:00:00 EST 2016 · Journal of Chemical Physics · OSTI ID:1371548

Fang, Yi; Liu, Fang; Barber, Victoria P.; +3 more

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

Journal Article · Wed Jul 27 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1371548

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.; +1 more

Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

Journal Article · Thu Jul 28 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1371548

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products

Citation Formats

References (34)

Cited By (6)

Similar Records

Related Subjects

Title: Tunneling effects in the unimolecular decay of (CH₃)₂COO Criegee intermediates to OH radical products