Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical
Abstract
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 ΔfH0K°(CH3) yields ΔfH0K°(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.
- Authors:
-
[3];
[3];
[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)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1485829
- Report Number(s):
- SAND-2018-13191J
Journal ID: ISSN 1948-7185; 670054
- Grant/Contract Number:
- AC04-94AL85000; NA0003525
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 3; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Voronova, Krisztina, Ervin, Kent M., Torma, Krisztián G., Hemberger, Patrick, Bodi, Andras, Gerber, Thomas, Osborn, David L., and Sztáray, Bálint. Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical. United States: N. p., 2017.
Web. doi:10.1021/acs.jpclett.7b03145.
Voronova, Krisztina, Ervin, Kent M., Torma, Krisztián G., Hemberger, Patrick, Bodi, Andras, Gerber, Thomas, Osborn, David L., & Sztáray, Bálint. Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical. United States. https://doi.org/10.1021/acs.jpclett.7b03145
Voronova, Krisztina, Ervin, Kent M., Torma, Krisztián G., Hemberger, Patrick, Bodi, Andras, Gerber, Thomas, Osborn, David L., and Sztáray, Bálint. Sun .
"Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical". United States. https://doi.org/10.1021/acs.jpclett.7b03145. https://www.osti.gov/servlets/purl/1485829.
@article{osti_1485829,
title = {Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical},
author = {Voronova, Krisztina and Ervin, Kent M. and Torma, Krisztián G. and Hemberger, Patrick and Bodi, Andras and Gerber, Thomas and Osborn, David L. and Sztáray, Bálint},
abstractNote = {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 ΔfH0K°(CH3) yields ΔfH0K°(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.},
doi = {10.1021/acs.jpclett.7b03145},
journal = {Journal of Physical Chemistry Letters},
number = 3,
volume = 9,
place = {United States},
year = {Sun Dec 31 00:00:00 EST 2017},
month = {Sun Dec 31 00:00:00 EST 2017}
}
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Figures / Tables:
Figure 1.: CH3+ and CH3OO+ kinetic traces in the presence of oxygen, integrated over the 10.24-11.31 eV photon energy range.
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