Isomer-resolved unimolecular dynamics of the hydroperoxyalkyl intermediate (•QOOH) in cyclohexane oxidation

Qian, Yujie; Roy, Tarun Kumar; Jasper, Ahren W.; Sojdak, Christopher A.; Kozlowski, Marisa C.; Klippenstein, Stephen J.; Lester, Marsha I.

doi:10.1073/pnas.2401148121

Title: Isomer-resolved unimolecular dynamics of the hydroperoxyalkyl intermediate (•QOOH) in cyclohexane oxidation

Journal Article · Thu Apr 11 00:00:00 EDT 2024 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2401148121· OSTI ID:2336631

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Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439

The oxidation of cycloalkanes is important in the combustion of transportation fuels and in atmospheric secondary organic aerosol formation. A transient carbon-centered radical intermediate (•QOOH) in the oxidation of cyclohexane is identified through its infrared fingerprint and time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) radical and bicyclic ether products. Although the cyclohexyl ring structure leads to three nearly degenerate •QOOH isomers (β-, γ-, and δ-QOOH), their transition state (TS) barriers to OH products are predicted to differ considerably. Selective characterization of the β-QOOH isomer is achieved at excitation energies associated with the lowest TS barrier, resulting in rapid unimolecular decay to OH products that are detected. A benchmarking approach is employed for the calculation of high-accuracy stationary point energies, in particular TS barriers, for cyclohexane oxidation (C ₆ H ₁₁ O ₂ ), building on higher-level reference calculations for the smaller ethane oxidation (C ₂ H ₅ O ₂ ) system. The isomer-specific characterization of β-QOOH is validated by comparison of experimental OH product appearance rates with computed statistical microcanonical rates, including significant heavy-atom tunneling, at energies in the vicinity of the TS barrier. Master-equation modeling is utilized to extend the results to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclohexane combustion.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-87ER13792; AC02-06CH11357

OSTI ID:: 2336631

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 121 Journal Issue: 16; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance Orlando, John J.; Tyndall, Geoffrey S. Chemical Society Reviews, Vol. 41, Issue 19 https://doi.org/10.1039/c2cs35166h	journal	January 2012
Atmospheric Chemistry of Cyclohexane: UV Spectra of c-C ₆ H ₁₁ ^• and (c-C ₆ H ₁₁ )O ₂ ^• Radicals, Kinetics of the Reactions of (c-C ₆ H ₁₁ )O ₂ ^• Radicals with NO and NO ₂ , and the Fate of the Alkoxy Radical (c-C ₆ H ₁₁ )O ^• Platz, J.; Sehested, J.; Nielsen, O. J. The Journal of Physical Chemistry A, Vol. 103, Issue 15 https://doi.org/10.1021/jp984195x	journal	March 1999
Theoretical Kinetic Study of the Reactions of Cycloalkylperoxy Radicals Sirjean, B.; Glaude, P. A.; Ruiz-Lòpez, M. F. The Journal of Physical Chemistry A, Vol. 113, Issue 25 https://doi.org/10.1021/jp901492e	journal	May 2009
Energy-resolved and time-dependent unimolecular dissociation of hydroperoxyalkyl radicals (˙QOOH) Bhagde, Trisha; Hansen, Anne S.; Chen, Shuguang Faraday Discussions, Vol. 238 https://doi.org/10.1039/D2FD00008C	journal	January 2022
Oxidation Flow Reactor Results in a Chinese Megacity Emphasize the Important Contribution of S/IVOCs to Ambient SOA Formation Hu, Weiwei; Zhou, Huaishan; Chen, Wei Environmental Science & Technology, Vol. 56, Issue 11 https://doi.org/10.1021/acs.est.1c03155	journal	December 2021
Ab initio evaluation of primary cyclo-hexane oxidation reaction rates Cavallotti, C.; Rota, R.; Faravelli, T. Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.07.195	journal	January 2007
Thermalized Epoxide Formation in the Atmosphere Møller, Kristian H.; Kurtén, Theo; Bates, Kelvin H. The Journal of Physical Chemistry A, Vol. 123, Issue 49 https://doi.org/10.1021/acs.jpca.9b09364	journal	November 2019
Insights into Constraining Rate Coefficients in Fuel Oxidation Mechanisms Using Genetic Algorithm Optimization Demireva, Maria; Sheps, Leonid; Hansen, Nils Energy & Fuels, Vol. 37, Issue 18 https://doi.org/10.1021/acs.energyfuels.3c02129	journal	September 2023
Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition Zádor, Judit; Huang, Haifeng; Welz, Oliver Physical Chemistry Chemical Physics, Vol. 15, Issue 26 https://doi.org/10.1039/c3cp51185e	journal	January 2013
Recent progress in the development of diesel surrogate fuels Pitz, William J.; Mueller, Charles J. Progress in Energy and Combustion Science, Vol. 37, Issue 3 https://doi.org/10.1016/j.pecs.2010.06.004	journal	June 2011
A comprehensive study on low-temperature oxidation chemistry of cyclohexane. I. Conformational analysis and theoretical study of first and second oxygen addition Zou, Jiabiao; Li, Yuyang; Ye, Lili Combustion and Flame, Vol. 235 https://doi.org/10.1016/j.combustflame.2021.111658	journal	January 2022
An experimental and modeling study of the low- and high-temperature oxidation of cyclohexane Serinyel, Zeynep; Herbinet, Olivier; Frottier, Ophélie Combustion and Flame, Vol. 160, Issue 11 https://doi.org/10.1016/j.combustflame.2013.05.016	journal	November 2013
Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations Bourgalais, Jérémy; Carstensen, Hans-Heinrich; Herbinet, Olivier The Journal of Physical Chemistry A, Vol. 126, Issue 34 https://doi.org/10.1021/acs.jpca.2c04490	journal	August 2022
Kinetics of elementary reactions in low-temperature autoignition chemistry Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X. Progress in Energy and Combustion Science, Vol. 37, Issue 4 https://doi.org/10.1016/j.pecs.2010.06.006	journal	August 2011
Secondary Organic Aerosol Formation from Acyclic, Monocyclic, and Polycyclic Alkanes Hunter, James F.; Carrasquillo, Anthony J.; Daumit, Kelly E. Environmental Science & Technology, Vol. 48, Issue 17 https://doi.org/10.1021/es502674s	journal	August 2014
Reactions of OH Radicals with C₆–C₁₀ Cycloalkanes in the Presence of NO: Isomerization of C₇–C₁₀ Cycloalkoxy Radicals Aschmann, Sara M.; Arey, Janet; Atkinson, Roger The Journal of Physical Chemistry A, Vol. 115, Issue 50 https://doi.org/10.1021/jp209654h	journal	November 2011
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
A theoretical study of cyclic ether formation reactions Bugler, John; Power, Jennifer; Curran, Henry J. Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.05.006	journal	January 2017
Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation† Silke, Emma J.; Pitz, William J.; Westbrook, Charles K. The Journal of Physical Chemistry A, Vol. 111, Issue 19 https://doi.org/10.1021/jp067592d	journal	May 2007
Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O ₂ : Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH ₃ ) ₃ COOH Whelan, Charlotte A.; Blitz, Mark A.; Shannon, Robin The Journal of Physical Chemistry A, Vol. 123, Issue 47 https://doi.org/10.1021/acs.jpca.9b08785	journal	October 2019
Observations of the Release of Non-methane Hydrocarbons from Fractured Shale Sommariva, Roberto; Blake, Robert S.; Cuss, Robert J. Environmental Science & Technology, Vol. 48, Issue 15 https://doi.org/10.1021/es502508w	journal	July 2014
Uniqueness in the low temperature oxidation of cycloalkanes Yang, Yi; Boehman, André L.; Simmie, John M. Combustion and Flame, Vol. 157, Issue 12 https://doi.org/10.1016/j.combustflame.2010.06.005	journal	December 2010
Vibrational spectroscopy and dissociation dynamics of cyclohexyl hydroperoxide Roy, Tarun Kumar; Qian, Yujie; Karlsson, Elizabeth Chemical Science https://doi.org/10.1039/D4SC00151F	journal	January 2024
Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry Osborn, David L. Annual Review of Physical Chemistry, Vol. 68, Issue 1 https://doi.org/10.1146/annurev-physchem-040215-112151	journal	May 2017
Microcanonical Rate Constants for Unimolecular Reactions in the Low-Pressure Limit Jasper, Ahren W. The Journal of Physical Chemistry A, Vol. 124, Issue 7 https://doi.org/10.1021/acs.jpca.9b10693	journal	January 2020
Reactivity Extrapolation from Small to Large Molecular Systems via Isodesmic Reactions for Transition States Knyazev, Vadim D. The Journal of Physical Chemistry A, Vol. 108, Issue 48 https://doi.org/10.1021/jp046953r	journal	November 2004
Hydroprocessing of Biorenewable Thermal Deoxygenation Oils Eaton, Scott J.; Beis, Sedat H.; Karunarathne, Sampath A. Energy & Fuels, Vol. 29, Issue 5 https://doi.org/10.1021/acs.energyfuels.5b00396	journal	April 2015
Theory, measurements, and modeling of OH and HO2 formation in the reaction of cyclohexyl radicals with O2 Knepp, Adam M.; Meloni, Giovanni; Jusinski, Leonard E. Physical Chemistry Chemical Physics, Vol. 9, Issue 31 https://doi.org/10.1039/b705934e	journal	January 2007
Exploring hydroperoxides in combustion: History, recent advances and perspectives Wang, Zhandong; Herbinet, Olivier; Hansen, Nils Progress in Energy and Combustion Science, Vol. 73 https://doi.org/10.1016/j.pecs.2019.02.003	journal	July 2019
Watching a hydroperoxyalkyl radical (•QOOH) dissociate Hansen, Anne S.; Bhagde, Trisha; Moore, Kevin B. Science, Vol. 373, Issue 6555 https://doi.org/10.1126/science.abj0412	journal	August 2021
A large source of low-volatility secondary organic aerosol Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard Nature, Vol. 506, Issue 7489 https://doi.org/10.1038/nature13032	journal	February 2014
Autoignition of cyclohexane at low-to-intermediate temperatures: Rapid compression machine experiments and improved comprehensive chemical kinetic model Chatterjee, Tanusree; Wang, Mengyuan; Wagnon, Scott W. Combustion and Flame, Vol. 259 https://doi.org/10.1016/j.combustflame.2023.113187	journal	January 2024
Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: the cyclohexyl + O2 reaction at high pressure Fernandes, Ravi X.; Zádor, Judit; Jusinski, Leonard E. Physical Chemistry Chemical Physics, Vol. 11, Issue 9 https://doi.org/10.1039/b819825j	journal	January 2009
Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH) Savee, John D.; Papajak, Ewa; Rotavera, Brandon Science, Vol. 347, Issue 6222 https://doi.org/10.1126/science.aaa1495	journal	February 2015
Hydroxyl Radical Recycling in Isoprene Oxidation Driven by Hydrogen Bonding and Hydrogen Tunneling: The Upgraded LIM1 Mechanism Peeters, Jozef; Müller, Jean-François; Stavrakou, Trissevgeni The Journal of Physical Chemistry A, Vol. 118, Issue 38 https://doi.org/10.1021/jp5033146	journal	July 2014
Infrared spectroscopic signature of a hydroperoxyalkyl radical (•QOOH) Hansen, Anne S.; Bhagde, Trisha; Qian, Yujie The Journal of Chemical Physics, Vol. 156, Issue 1 https://doi.org/10.1063/5.0076505	journal	January 2022
Gas-Phase Chlorine Radical Oxidation of Alkanes: Effects of Structural Branching, NO_x, and Relative Humidity Observed during Environmental Chamber Experiments Jahn, Leif G.; Wang, Dongyu S.; Dhulipala, Surya Venkatesh The Journal of Physical Chemistry A, Vol. 125, Issue 33 https://doi.org/10.1021/acs.jpca.1c03516	journal	August 2021
The Stability of α-Hydroperoxyalkyl Radicals Anglada, Josep M.; Crehuet, Ramon; Francisco, Joseph S. Chemistry - A European Journal, Vol. 22, Issue 50 https://doi.org/10.1002/chem.201604499	journal	November 2016
High-Accuracy Heats of Formation for Alkane Oxidation: From Small to Large via the Automated CBH-ANL Method Elliott, Sarah N.; Keçeli, Murat; Ghosh, Manik K. The Journal of Physical Chemistry A, Vol. 127, Issue 6 https://doi.org/10.1021/acs.jpca.2c07248	journal	January 2023
Chamber-based insights into the factors controlling epoxydiol (IEPOX) secondary organic aerosol (SOA) yield, composition, and volatility D'Ambro, Emma L.; Schobesberger, Siegfried; Gaston, Cassandra J. Atmospheric Chemistry and Physics, Vol. 19, Issue 17 https://doi.org/10.5194/acp-19-11253-2019	journal	January 2019
Accretion Product Formation from Ozonolysis and OH Radical Reaction of α-Pinene: Mechanistic Insight and the Influence of Isoprene and Ethylene Berndt, Torsten; Mentler, Bernhard; Scholz, Wiebke Environmental Science & Technology, Vol. 52, Issue 19 https://doi.org/10.1021/acs.est.8b02210	journal	September 2018
Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NO _x Lim, Yong B.; Ziemann, Paul J. Environmental Science & Technology, Vol. 43, Issue 7 https://doi.org/10.1021/es803389s	journal	April 2009
A comprehensive study on low-temperature oxidation chemistry of cyclohexane. II. Experimental and kinetic modeling investigation Zou, Jiabiao; Jin, Hanfeng; Liu, Dapeng Combustion and Flame, Vol. 235 https://doi.org/10.1016/j.combustflame.2021.111550	journal	January 2022
Role of O ₂ + QOOH in Low-Temperature Ignition of Propane. 1. Temperature and Pressure Dependent Rate Coefficients Goldsmith, C. Franklin; Green, William H.; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 116, Issue 13 https://doi.org/10.1021/jp210722w	journal	March 2012
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
Development of an advanced, thermally stable, coal-based jet fuel Balster, Lori M.; Corporan, Edwin; DeWitt, Matthew J. Fuel Processing Technology, Vol. 89, Issue 4 https://doi.org/10.1016/j.fuproc.2007.11.018	journal	April 2008
Systematic Computational Study on the Unimolecular Reactions of Alkylperoxy (RO ₂ ), Hydroperoxyalkyl (QOOH), and Hydroperoxyalkylperoxy (O ₂ QOOH) Radicals Miyoshi, Akira The Journal of Physical Chemistry A, Vol. 115, Issue 15 https://doi.org/10.1021/jp112152n	journal	April 2011
Compositional effects on the ignition of FACE gasolines Sarathy, S. Mani; Kukkadapu, Goutham; Mehl, Marco Combustion and Flame, Vol. 169 https://doi.org/10.1016/j.combustflame.2016.04.010	journal	July 2016
Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene Paulot, F.; Crounse, J. D.; Kjaergaard, H. G. Science, Vol. 325, Issue 5941 https://doi.org/10.1126/science.1172910	journal	August 2009

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