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

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

doi:10.1063/1.4972015

Title: 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

DOI:https://doi.org/10.1063/1.4972015· OSTI ID:1373744

Fang, Yi ^[1];

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

^[2];

^[3]; Lester, Marsha I. ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

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. 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. Finally, thermal unimolecular decay of syn-CH₃CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.

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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). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-06CH11357; CHE-1362835; CHE-1619660

OSTI ID:: 1373744

Alternate ID(s):: OSTI ID: 1336837

Journal Information:: Journal of Chemical Physics, Vol. 145, Issue 23; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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References (52)

Improved Multidimensional Semiclassical Tunneling Theory Wagner, Albert F. The Journal of Physical Chemistry A, Vol. 117, Issue 49 https://doi.org/10.1021/jp409720s	journal	November 2013
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
Known and Unexplored Organic Constituents in the Earth's Atmosphere Goldstein, Allen H.; Galbally, Ian E. Environmental Science & Technology, Vol. 41, Issue 5 https://doi.org/10.1021/es072476p	journal	March 2007
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
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
Connecting Chemical Dynamics in Gases and Liquids Elles, Christopher G.; Crim, F. Fleming Annual Review of Physical Chemistry, Vol. 57, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104538	journal	May 2006
Fourier-transform microwave spectroscopy of an alkyl substituted Criegee intermediate anti-CH3CHOO Nakajima, Masakazu; Yue, Qiang; Endo, Yasuki Journal of Molecular Spectroscopy, Vol. 310 https://doi.org/10.1016/j.jms.2014.11.004	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 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
Total radical yields from tropospheric ethene ozonolysis Alam, Mohammed S.; Camredon, Marie; Rickard, Andrew R. Physical Chemistry Chemical Physics, Vol. 13, Issue 23 https://doi.org/10.1039/c0cp02342f	journal	January 2011
A transition state theory‐based statistical distribution of unimolecular decay rates with application to unimolecular decomposition of formaldehyde Miller, William H.; Hernandez, Rigoberto; Moore, C. Bradley The Journal of Chemical Physics, Vol. 93, Issue 8 https://doi.org/10.1063/1.459636	journal	October 1990
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
Kinetic and Theoretical Investigation of the Gas-Phase Ozonolysis of Isoprene: Carbonyl Oxides as an Important Source for OH Radicals in the Atmosphere Gutbrod, Roland; Kraka, Elfi; Schindler, Ralph N. Journal of the American Chemical Society, Vol. 119, Issue 31 https://doi.org/10.1021/ja970050c	journal	August 1997
Ab initio calculation of anharmonic constants for a transition state, with application to semiclassical transition state tunneling probabilities Miller, William H.; Hernandez, Rigoberto; Handy, Nicholas C. Chemical Physics Letters, Vol. 172, Issue 1 https://doi.org/10.1016/0009-2614(90)87217-F	journal	August 1990
Night-time radical chemistry during the TORCH campaign Emmerson, K. M.; Carslaw, N. Atmospheric Environment, Vol. 43, Issue 20 https://doi.org/10.1016/j.atmosenv.2009.03.042	journal	June 2009
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
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
A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C. The Journal of Chemical Physics, Vol. 142, Issue 12 https://doi.org/10.1063/1.4914987	journal	March 2015
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
MRCISD Studies of the Dissociation of Vinylhydroperoxide, CH ₂ CHOOH: There Is a Saddle Point Kurtén, Theo; Donahue, Neil M. The Journal of Physical Chemistry A, Vol. 116, Issue 25 https://doi.org/10.1021/jp302511a	journal	May 2012
Direct Kinetic Measurements of Criegee Intermediate (CH2OO) Formed by Reaction of CH2I with O2 Welz, O.; Savee, J. D.; Osborn, D. L. Science, Vol. 335, Issue 6065 https://doi.org/10.1126/science.1213229	journal	January 2012
The addition and dissociation reaction atomic hydrogen + carbon monoxide .dblharw. oxomethyl. 1. Theoretical RRKM studies Wagner, Albert F.; Bowman, Joel M. The Journal of Physical Chemistry, Vol. 91, Issue 20 https://doi.org/10.1021/j100304a036	journal	September 1987
Impact of the water dimer on the atmospheric reactivity of carbonyl oxides Anglada, Josep M.; Solé, Albert Physical Chemistry Chemical Physics, Vol. 18, Issue 26 https://doi.org/10.1039/C6CP02531E	journal	January 2016
A practical implementation of semi-classical transition state theory for polyatomics Nguyen, Thanh Lam; Stanton, John F.; Barker, John R. Chemical Physics Letters, Vol. 499, Issue 1-3 https://doi.org/10.1016/j.cplett.2010.09.015	journal	October 2010
The reactions of ozone with alkenes: An important source of HO _x in the boundary layer Paulson, Suzanne E.; Orlando, John J. Geophysical Research Letters, Vol. 23, Issue 25 https://doi.org/10.1029/96GL03477	journal	December 1996
Tropospheric OH and HO2 radicals: field measurements and model comparisons Stone, Daniel; Whalley, Lisa K.; Heard, Dwayne E. Chemical Society Reviews, Vol. 41, Issue 19 https://doi.org/10.1039/c2cs35140d	journal	January 2012
Theoretical/experimental comparison of deep tunneling decay of quasi-bound H(D)OCO to H(D) + CO ₂ Wagner, Albert F.; Dawes, Richard; Continetti, Robert E. The Journal of Chemical Physics, Vol. 141, Issue 5 https://doi.org/10.1063/1.4891675	journal	August 2014
Direct observation of OH formation from stabilised Criegee intermediates Novelli, A.; Vereecken, L.; Lelieveld, J. Phys. Chem. Chem. Phys., Vol. 16, Issue 37 https://doi.org/10.1039/C4CP02719A	journal	January 2014
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
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon Woon, David E.; Dunning, Thom H. The Journal of Chemical Physics, Vol. 103, Issue 11 https://doi.org/10.1063/1.470645	journal	September 1995
Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH, HO2 and RO2 Emmerson, K. M.; Carslaw, N.; Pilling, M. J. Journal of Atmospheric Chemistry, Vol. 52, Issue 2 https://doi.org/10.1007/s10874-005-1323-2	journal	October 2005
UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH ₃ CHOO Beames, Joseph M.; Liu, Fang; Lu, Lu The Journal of Chemical Physics, Vol. 138, Issue 24 https://doi.org/10.1063/1.4810865	journal	June 2013
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
The physical chemistry of Criegee intermediates in the gas phase Osborn, David L.; Taatjes, Craig A. International Reviews in Physical Chemistry, Vol. 34, Issue 3 https://doi.org/10.1080/0144235X.2015.1055676	journal	July 2015
Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn -CH ₃ CHOO through pure rotational transitions Nakajima, Masakazu; Endo, Yasuki The Journal of Chemical Physics, Vol. 140, Issue 1 https://doi.org/10.1063/1.4861494	journal	January 2014
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
Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar Peterson, Kirk A.; Adler, Thomas B.; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 128, Issue 8 https://doi.org/10.1063/1.2831537	journal	February 2008
UV absorption probing of the conformer-dependent reactivity of a Criegee intermediate CH ₃ CHOO Sheps, Leonid; Scully, Ashley M.; Au, Kendrew Phys. Chem. Chem. Phys., Vol. 16, Issue 48 https://doi.org/10.1039/C4CP04408H	journal	January 2014
A random matrix/transition state theory for the probability distribution of state‐specific unimolecular decay rates: Generalization to include total angular momentum conservation and other dynamical symmetries Hernandez, Rigoberto; Miller, William H.; Moore, C. Bradley The Journal of Chemical Physics, Vol. 99, Issue 2 https://doi.org/10.1063/1.465360	journal	July 1993
Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO Taatjes, C. A.; Welz, O.; Eskola, A. J. Science, Vol. 340, Issue 6129 https://doi.org/10.1126/science.1234689	journal	April 2013
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
Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products Liu, F.; Beames, J. M.; Petit, A. S. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1257158	journal	September 2014
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
Harmonic and Anharmonic Vibrational Frequency Calculations with the Double-Hybrid B2PLYP Method: Analytic Second Derivatives and Benchmark Studies Biczysko, Malgorzata; Panek, Pawel; Scalmani, Giovanni Journal of Chemical Theory and Computation, Vol. 6, Issue 7 https://doi.org/10.1021/ct100212p	journal	June 2010
DSD-BLYP: A General Purpose Double Hybrid Density Functional Including Spin Component Scaling and Dispersion Correction Kozuch, Sebastian; Gruzman, David; Martin, Jan M. L. The Journal of Physical Chemistry C, Vol. 114, Issue 48 https://doi.org/10.1021/jp1070852	journal	October 2010
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
Free radical modelling studies during the UK TORCH Campaign in Summer 2003 Emmerson, K. M.; Carslaw, N.; Carslaw, D. C. Atmospheric Chemistry and Physics, Vol. 7, Issue 1 https://doi.org/10.5194/acp-7-167-2007	journal	January 2007
Communication: New insight into the barrier governing CO2 formation from OH + CO Johnson, Christopher J.; Poad, Berwyck L. J.; Shen, Ben B. The Journal of Chemical Physics, Vol. 134, Issue 17 https://doi.org/10.1063/1.3589860	journal	May 2011

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