Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical

Voronova, Krisztina; Ervin, Kent M.; Torma, Krisztián G.; Hemberger, Patrick; Bodi, Andras; Gerber, Thomas; Osborn, David L.; Sztáray, Bálint

doi:10.1021/acs.jpclett.7b03145

Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical

Journal Article · Sat Dec 30 23:00:00 EST 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b03145· OSTI ID:1485829

Voronova, Krisztina ^[1]; Ervin, Kent M. ^[2]; Torma, Krisztián G. ^[1]; ^[3]; ^[3]; Gerber, Thomas ^[3]; Osborn, David L. ^[4]; ^[1]

Univ. of the Pacific, Stockton, CA (United States)
Univ. of Nevada, Reno, NV (United States)
Paul Scherrer Institute, Villigen PSI (Switzerland)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)

In this study, we investigated the simplest alkylperoxy radical, CH₃OO, formed by reacting photolytically generated CH₃ radicals with O₂, using the new combustion reactions followed by photoelectron photoion coincidence (CRF-PEPICO) apparatus at the Swiss Light Source. Modeling the experimental photoion mass-selected threshold photoelectron spectrum using Franck–Condon simulations including transitions to triplet and singlet cationic states yielded the adiabatic ionization energy of 10.265 ± 0.025 eV. Dissociative photoionization of CH₃OO generates the CH₃⁺ fragment ion at the appearance energy of 11.164 ± 0.010 eV. Combining these two values with Δ_fH_0K°(CH₃) yields Δ_fH_0K°(CH₃OO) = 22.06 ± 0.97 kJ mol^–1, reducing the uncertainty of the previously determined value by a factor of 5. Lastly, statistical simulation of the CH₃OO breakdown diagram provides a molecular thermometer of the free radical’s internal temperature, which we measured to be 330 ± 30 K.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1485829

Report Number(s):: SAND--2018-13191J; 670054

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 3 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Isomer-Selective Generation and Spectroscopic Characterization of Picolyl Radicals Reusch, Engelbert; Holzmeier, Fabian; Constantinidis, Philipp Angewandte Chemie International Edition, Vol. 56, Issue 27 https://doi.org/10.1002/anie.201703433	journal	June 2017
Modeling unimolecular reactions in photoelectron photoion coincidence experiments Sztáray, Bálint; Bodi, Andras; Baer, Tomas Journal of Mass Spectrometry, Vol. 45, Issue 11 https://doi.org/10.1002/jms.1813	journal	September 2010
Synchrotron threshold photoelectron photoion coincidence spectroscopy of radicals produced in a pyrolysis source: The methyl radical Zhu, Yupeng; Wu, Xiangkun; Tang, Xiaofeng Chemical Physics Letters, Vol. 664 https://doi.org/10.1016/j.cplett.2016.10.041	journal	November 2016
Photoionization and dissociative photoionization of the allyl radical, C3H5 Fischer, Ingo; Schüßler, Thomas; Deyerl, Hans-Jürgen International Journal of Mass Spectrometry, Vol. 261, Issue 2-3 https://doi.org/10.1016/j.ijms.2006.09.023	journal	March 2007
Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates Battin-Leclerc, F. Progress in Energy and Combustion Science, Vol. 34, Issue 4 https://doi.org/10.1016/j.pecs.2007.10.002	journal	August 2008
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
Manifestations of Torsion-CH Stretch Coupling in the Infrared Spectrum of CH ₃ OO Hsu, Kuo-Hsiang; Huang, Yu-Hsuan; Lee, Yuan-Pern The Journal of Physical Chemistry A, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpca.5b12334	journal	February 2016
Negative-Ion Photoelectron Spectroscopy, Gas-Phase Acidity, and Thermochemistry of the Peroxyl Radicals CH ₃ OO and CH ₃ CH ₂ OO Blanksby, Stephen J.; Ramond, Tanya M.; Davico, Gustavo E. Journal of the American Chemical Society, Vol. 123, Issue 39 https://doi.org/10.1021/ja010942j	journal	October 2001
Energy-Resolved Photoionization of Alkylperoxy Radicals and the Stability of Their Cations Meloni, Giovanni; Zou, Peng; Klippenstein, Stephen J. Journal of the American Chemical Society, Vol. 128, Issue 41 https://doi.org/10.1021/ja064556j	journal	October 2006
Photoelectron Spectrum and Energetics of the meta -Xylylene Diradical Steglich, Mathias; Custodis, Victoria B. F.; Trevitt, Adam J. Journal of the American Chemical Society, Vol. 139, Issue 41 https://doi.org/10.1021/jacs.7b06714	journal	October 2017
Naphthyl Radical: Negative Ion Photoelectron Spectroscopy, Franck−Condon Simulation, and Thermochemistry Ervin, Kent M.; Ramond, Tanya M.; Davico, Gustavo E. The Journal of Physical Chemistry A, Vol. 105, Issue 48 https://doi.org/10.1021/jp011779h	journal	November 2001
A Halomethane Thermochemical Network from iPEPICO Experiments and Quantum Chemical Calculations Harvey, Jonelle; Tuckett, Richard P.; Bodi, Andras The Journal of Physical Chemistry A, Vol. 116, Issue 39 https://doi.org/10.1021/jp307941k	journal	September 2012
Mass-Resolved Isomer-Selective Chemical Analysis with Imaging Photoelectron Photoion Coincidence Spectroscopy Bodi, Andras; Hemberger, Patrick; Osborn, David L. The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401500c	journal	August 2013
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
Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15946	journal	June 2017
The VUV photochemistry of radicals: C ₃ H ₃ and C ₂ H ₅ Schüßler, T.; Roth, W.; Gerber, T. Phys. Chem. Chem. Phys., Vol. 7, Issue 5 https://doi.org/10.1039/B414163F	journal	January 2005
Photoelectron–photoion coincidence spectroscopy for multiplexed detection of intermediate species in a flame Krüger, Julia; Garcia, Gustavo A.; Felsmann, Daniel Phys. Chem. Chem. Phys., Vol. 16, Issue 41 https://doi.org/10.1039/C4CP02857K	journal	January 2014
On the protonation of water Bodi, A.; Csontos, J.; Kállay, M. Chem. Sci., Vol. 5, Issue 8 https://doi.org/10.1039/C4SC00791C	journal	January 2014
Controlling tunnelling in methane loss from acetone ions by deuteration Bodi, Andras; Baer, Tomas; Wells, Nancy K. Physical Chemistry Chemical Physics, Vol. 17, Issue 43 https://doi.org/10.1039/C5CP02944A	journal	January 2015
On the absolute photoionization cross section and dissociative photoionization of cyclopropenylidene Holzmeier, Fabian; Fischer, Ingo; Kiendl, Benjamin Physical Chemistry Chemical Physics, Vol. 18, Issue 13 https://doi.org/10.1039/C6CP01068G	journal	January 2016
Advances in threshold photoelectron spectroscopy (TPES) and threshold photoelectron photoion coincidence (TPEPICO) Baer, Tomas; Tuckett, Richard P. Physical Chemistry Chemical Physics, Vol. 19, Issue 15 https://doi.org/10.1039/C7CP00144D	journal	January 2017
Dissociative photoionization mechanism of methanol isotopologues (CH3OH, CD3OH, CH3OD and CD3OD) by iPEPICO: energetics, statistical and non-statistical kinetics and isotope effects Borkar, Sampada; Sztáray, Bálint; Bodi, Andras Physical Chemistry Chemical Physics, Vol. 13, Issue 28 https://doi.org/10.1039/c1cp21015g	journal	January 2011
Suppression of hot electrons in threshold photoelectron photoion coincidence spectroscopy using velocity focusing optics Sztáray, Bálint; Baer, Tomas Review of Scientific Instruments, Vol. 74, Issue 8 https://doi.org/10.1063/1.1593788	journal	August 2003
Rovibrational photoionization dynamics of methyl and its isotopomers studied by high-resolution photoionization and photoelectron spectroscopy Schulenburg, A. M.; Alcaraz, Ch.; Grassi, G. The Journal of Chemical Physics, Vol. 125, Issue 10 https://doi.org/10.1063/1.2348875	journal	September 2006
Effect of methyl rotation on the electronic spectrum of the methyl peroxy radical Just, Gabriel M. P.; McCoy, Anne B.; Miller, Terry A. The Journal of Chemical Physics, Vol. 127, Issue 4 https://doi.org/10.1063/1.2747613	journal	July 2007
Data acquisition schemes for continuous two-particle time-of-flight coincidence experiments Bodi, Andras; Sztáray, Bálint; Baer, Tomas Review of Scientific Instruments, Vol. 78, Issue 8 https://doi.org/10.1063/1.2776012	journal	August 2007
The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics Osborn, David L.; Zou, Peng; Johnsen, Howard Review of Scientific Instruments, Vol. 79, Issue 10 https://doi.org/10.1063/1.3000004	journal	October 2008
A versatile electron-ion coincidence spectrometer for photoelectron momentum imaging and threshold spectroscopy on mass selected ions using synchrotron radiation Garcia, Gustavo A.; Soldi-Lose, Héloïse; Nahon, Laurent Review of Scientific Instruments, Vol. 80, Issue 2 https://doi.org/10.1063/1.3079331	journal	February 2009
Imaging photoelectron photoion coincidence spectroscopy with velocity focusing electron optics Bodi, Andras; Johnson, Melanie; Gerber, Thomas Review of Scientific Instruments, Vol. 80, Issue 3 https://doi.org/10.1063/1.3082016	journal	March 2009
A threshold photoelectron-photoion coincidence spectrometer with double velocity imaging using synchrotron radiation Tang, Xiaofeng; Zhou, Xiaoguo; Niu, Mingli Review of Scientific Instruments, Vol. 80, Issue 11 https://doi.org/10.1063/1.3250872	journal	November 2009
A new double imaging velocity focusing coincidence experiment: i ² PEPICO Bodi, Andras; Hemberger, Patrick; Gerber, Thomas Review of Scientific Instruments, Vol. 83, Issue 8 https://doi.org/10.1063/1.4742769	journal	August 2012
Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean-François The Journal of Chemical Physics, Vol. 142, Issue 16 https://doi.org/10.1063/1.4918634	journal	April 2015
Breaking through the false coincidence barrier in electron–ion coincidence experiments Osborn, David L.; Hayden, Carl C.; Hemberger, Patrick The Journal of Chemical Physics, Vol. 145, Issue 16 https://doi.org/10.1063/1.4965428	journal	October 2016
CRF-PEPICO: Double velocity map imaging photoelectron photoion coincidence spectroscopy for reaction kinetics studies Sztáray, Bálint; Voronova, Krisztina; Torma, Krisztián G. The Journal of Chemical Physics, Vol. 147, Issue 1 https://doi.org/10.1063/1.4984304	journal	July 2017
Examining the ground and first excited states of methyl peroxy radical with high-level coupled-cluster theory Copan, Andreas V.; Schaefer, Henry F.; Agarwal, Jay Molecular Physics, Vol. 113, Issue 19-20 https://doi.org/10.1080/00268976.2015.1063729	journal	July 2015
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
Interception of Excited Vibrational Quantum States by O2 in Atmospheric Association Reactions Glowacki, D. R.; Lockhart, J.; Blitz, M. A. Science, Vol. 337, Issue 6098 https://doi.org/10.1126/science.1224106	journal	August 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
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
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
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

Cited By (10)

A vacuum ultraviolet photoionization time-of-flight mass spectrometer with high sensitivity for study of gas-phase radical reaction in a flow tube Wen, Zuoying; Tang, Xiaofeng; Wang, Chengcheng International Journal of Chemical Kinetics, Vol. 51, Issue 3 https://doi.org/10.1002/kin.21241	journal	December 2018
Valence Photoionization of Thymine: Ionization Energies, Vibrational Structure, and Fragmentation Pathways from the Slow to the Ultrafast Majer, Katharina; Signorell, Ruth; Heringa, Maarten F. Chemistry – A European Journal, Vol. 25, Issue 62 https://doi.org/10.1002/chem.201903282	journal	October 2019
Kinetics of the a-C ₃ H ₅ + O ₂ reaction, investigated by photoionization using synchrotron radiation Schleier, D.; Constantinidis, P.; Faßheber, N. Physical Chemistry Chemical Physics, Vol. 20, Issue 16 https://doi.org/10.1039/c7cp07893e	journal	January 2018
Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions Covert, Kyle J.; Voronova, Krisztina; Torma, Krisztián G. Physical Chemistry Chemical Physics, Vol. 20, Issue 32 https://doi.org/10.1039/c8cp03168a	journal	January 2018
Metamorphic meta isomer: carbon dioxide and ketenes are formed via retro-Diels–Alder reactions in the decomposition of meta -benzenediol Gerlach, Marius; Bodi, Andras; Hemberger, Patrick Physical Chemistry Chemical Physics, Vol. 21, Issue 35 https://doi.org/10.1039/c9cp03519b	journal	January 2019
The ionization energy of the vinyl radical: a Mexican standoff with a happy ending Wu, Xiangkun; Zhou, Xiaoguo; Hemberger, Patrick Physical Chemistry Chemical Physics, Vol. 21, Issue 40 https://doi.org/10.1039/c9cp04493k	journal	January 2019
A guinea pig for conformer selectivity and mechanistic insights into dissociative ionization by photoelectron photoion coincidence: fluorocyclohexane Wu, Xiangkun; Zhou, Xiaoguo; Hemberger, Patrick Physical Chemistry Chemical Physics, Vol. 22, Issue 4 https://doi.org/10.1039/c9cp05617c	journal	January 2020
Photoelectron spectroscopy of boron-containing reactive intermediates using synchrotron radiation: BH ₂ , BH, and BF Mukhopadhyay, D. P.; Schleier, D.; Fischer, I. Physical Chemistry Chemical Physics, Vol. 22, Issue 3 https://doi.org/10.1039/c9cp06010c	journal	January 2020
Threshold Dissociation of the 1-ethynylpyrene Cation at Internal Energies Relevant to H i Regions Rouillé, Gaël; Steglich, Mathias; Hemberger, Patrick The Astrophysical Journal, Vol. 885, Issue 1 https://doi.org/10.3847/1538-4357/ab4418	journal	October 2019
Valence Photoionization of Thymine: Ionization Energies, Vibrational Structure, and Fragmentation Pathways from the Slow to the Ultrafast Katharina, Majer,; Ruth, Signorell,; F., Heringa, Maarten ETH Zurich https://doi.org/10.3929/ethz-b-000372255	text	January 2019

Figures / Tables (4)

Similar Records

Generation and detection of alkyl peroxy radicals in a supersonic jet expansion

Journal Article · Fri Jul 07 00:00:00 EDT 2006 · Journal of Chemical Physics · OSTI ID:20864265

A photoelectron-photoion coincidence study in the ICH{sub 2}CN ion dissociation: Thermochemistry of {sup {sm{underscore}bullet}}CH{sub 2}CN, {sup +}CH{sub 2}CN, and ICH{sub 2}CN

Journal Article · Wed Feb 23 23:00:00 EST 2000 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory · OSTI ID:20017292

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Journal Article · Fri Jul 20 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1485834

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical

Citation Formats

References (41)

Cited By (10)

Figures / Tables (4)

Similar Records

Related Subjects