Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes

Lester, Marsha I.; Klippenstein, Stephen J.

doi:10.1021/acs.accounts.8b00077

Title: Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes

Journal Article · Tue Apr 03 00:00:00 EDT 2018 · Accounts of Chemical Research

DOI:https://doi.org/10.1021/acs.accounts.8b00077· OSTI ID:1461467

^[1];

^[2]

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

Alkene ozonolysis is a primary oxidation pathway for anthropogenic and biogenic alkenes emitted into the troposphere. It is also an important source of atmospheric hydroxyl (OH) radicals, often called the atmosphere's detergent. Alkene ozonolysis takes place through a highly exothermic reaction pathway with multiple intermediates and barriers prior to releasing the OH radical products. Here, this Account focuses on a key reaction intermediate with a carbonyl oxide functional group (-COO), known as the Criegee intermediate, which is formed along with a carbonyl coproduct in alkene ozonolysis reactions. Under atmospheric conditions, the initially energized Criegee intermediates may promptly decay to OH products or be collisionally stabilized prior to thermal decay to OH radicals and other products.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461467

Journal Information:: Accounts of Chemical Research, Vol. 51, Issue 4; ISSN 0001-4842

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 81 works

Citation information provided by
Web of Science

References (50)

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
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
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
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
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
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
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
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
Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides Taatjes, Craig A. Annual Review of Physical Chemistry, Vol. 68, Issue 1 https://doi.org/10.1146/annurev-physchem-052516-050739	journal	May 2017
Structure-dependent reactivity of Criegee intermediates studied with spectroscopic methods Jr-Min Lin, Jim; Chao, Wen Chemical Society Reviews, Vol. 46, Issue 24 https://doi.org/10.1039/C7CS00336F	journal	January 2017
Formation of highly oxidized multifunctional compounds: autoxidation of peroxy radicals formed in the ozonolysis of alkenes – deduced from structure–product relationships Mentel, T. F.; Springer, M.; Ehn, M. Atmospheric Chemistry and Physics, Vol. 15, Issue 12 https://doi.org/10.5194/acp-15-6745-2015	journal	January 2015
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
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
Measurement and modelling of air pollution and atmospheric chemistry in the U.K. West Midlands conurbation: Overview of the PUMA Consortium project Harrison, R. M.; Yin, J.; Tilling, R. M. Science of The Total Environment, Vol. 360, Issue 1-3 https://doi.org/10.1016/j.scitotenv.2005.08.053	journal	May 2006
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
The Pressure Dependence of the OH Radical Yield from Ozone−Alkene Reactions Fenske, Jill D.; Hasson, Alam S.; Paulson, Suzanne E. The Journal of Physical Chemistry A, Vol. 104, Issue 33 https://doi.org/10.1021/jp001100u	journal	August 2000
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
Tunneling effects in the unimolecular decay of (CH ₃ ) ₂ COO Criegee intermediates to OH radical products Fang, Yi; Barber, Victoria P.; Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 146, Issue 13 https://doi.org/10.1063/1.4979297	journal	April 2017
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 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
Unimolecular Decay of the Dimethyl-Substituted Criegee Intermediate in Alkene Ozonolysis: Decay Time Scales and the Importance of Tunneling Drozd, Greg T.; Kurtén, Theo; Donahue, Neil M. The Journal of Physical Chemistry A, Vol. 121, Issue 32 https://doi.org/10.1021/acs.jpca.7b05495	journal	August 2017
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 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
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 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
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
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
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
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
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
Ultraviolet Spectrum and Photochemistry of the Simplest Criegee Intermediate CH ₂ OO Beames, Joseph M.; Liu, Fang; Lu, Lu Journal of the American Chemical Society, Vol. 134, Issue 49 https://doi.org/10.1021/ja310603j	journal	December 2012
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
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
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
Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO ₂ , H ₂ O and decomposition under boundary layer conditions Newland, Mike J.; Rickard, Andrew R.; Alam, Mohammed S. Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP04186K	journal	January 2015
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
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 decay strongly limits the atmospheric impact of Criegee intermediates Vereecken, L.; Novelli, A.; Taraborrelli, D. Physical Chemistry Chemical Physics, Vol. 19, Issue 47 https://doi.org/10.1039/C7CP05541B	journal	January 2017
The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere Vereecken, L.; Harder, H.; Novelli, A. Physical Chemistry Chemical Physics, Vol. 14, Issue 42 https://doi.org/10.1039/c2cp42300f	journal	January 2012
Research frontiers in the chemistry of Criegee intermediates and tropospheric ozonolysis Taatjes, Craig A.; Shallcross, Dudley E.; Percival, Carl J. Physical Chemistry Chemical Physics, Vol. 16, Issue 5 https://doi.org/10.1039/c3cp52842a	journal	January 2014
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
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
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
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
Pressure-Dependent Criegee Intermediate Stabilization from Alkene Ozonolysis Hakala, Jani P.; Donahue, Neil M. The Journal of Physical Chemistry A, Vol. 120, Issue 14 https://doi.org/10.1021/acs.jpca.6b01538	journal	April 2016
Hydroxyacetone Production From C ₃ Criegee Intermediates Taatjes, Craig A.; Liu, Fang; Rotavera, Brandon The Journal of Physical Chemistry A, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpca.6b07712	journal	December 2016
Quantum Chemical and Statistical Rate Theory Studies of the Vinyl Hydroperoxides Formed in trans -2-Butene and 2,3-Dimethyl-2-butene Ozonolysis Kuwata, Keith T.; Luu, Lina; Weberg, Alexander B. The Journal of Physical Chemistry A, Vol. 122, Issue 9 https://doi.org/10.1021/acs.jpca.8b00287	journal	February 2018
Predictive a priori pressure-dependent kinetics Jasper, Ahren W.; Pelzer, Kenley M.; Miller, James A. Science, Vol. 346, Issue 6214 https://doi.org/10.1126/science.1260856	journal	December 2014

Cited By (6)

Formation of Criegee intermediates and peroxy acids: a computational study of gas-phase 1,3-cycloaddition of ozone with catechol Deb, Debojit Kumar; Sarkar, Biplab Physical Chemistry Chemical Physics, Vol. 21, Issue 27 https://doi.org/10.1039/c9cp01312a	journal	January 2019
Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09948-7	journal	May 2019
Fourier-transform microwave spectroscopy on weakly bound complexes of CH ₂ OO with Ar, CO, and N ₂ Nakajima, Masakazu; Endo, Yasuki The Journal of Chemical Physics, Vol. 151, Issue 6 https://doi.org/10.1063/1.5116165	journal	August 2019
Threshold photoelectron spectrum of the CH 2 OO Criegee intermediate Chicharro, David V.; Poullain, Sonia Marggi; Bañares, Luis Physical Chemistry Chemical Physics, Vol. 21, Issue 24 https://doi.org/10.1039/c9cp02538c	journal	January 2019
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
DFT studies on quantum mechanical tunneling in tautomerization of three-membered rings Jana, Kalyanashis; Ganguly, Bishwajit Physical Chemistry Chemical Physics, Vol. 20, Issue 44 https://doi.org/10.1039/c8cp03963a	journal	January 2018

Similar Records

Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products

Journal Article · Wed Feb 10 00:00:00 EST 2016 · Journal of Chemical Physics · OSTI ID:1461467

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:1461467

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:1461467

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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes

Citation Formats

References (50)

Cited By (6)

Similar Records

Related Subjects