Ground and low-lying excited states of phenoxy, 1-naphthoxy, and 2-naphthoxy radicals via anion photoelectron spectroscopy
Abstract
Here, we present the slow electron velocity map imaging spectroscopy of cryogenically cooled phenoxide, 1-naphthoxide, and 2-naphthoxide anions. The results allow us to examine the ground state and the lowest energy excited state in the corresponding neutral radicals. Care was taken to minimize autodetachment signals in the photoelectron spectra, allowing for more straightforward comparisons with Franck-Condon analyses. The ground states of these three aromatic oxide radicals all have the unpaired electron residing in a π orbital delocalized throughout the molecule. The electron affinity of 1-naphthoxy is measured to be 2.290(2) eV, while that of 2-naphthoxy is measured to be 2.404(2) eV, both of which are higher than that of the smaller phenoxy molecule at 2.253(1) eV. The first excited states have the unpaired electron residing in a more localized σ orbital, yielding measured term energies for the à state of 1.237(2) eV in 1-naphthoxy and 1.068(1) eV in 2-naphthoxy, while that of phenoxy is lower at 0.952(1) eV. The calculated Franck-Condon spectra generally showed good agreement with the experimental spectra, yielding assignments of the more active vibrations in each electronic state. Significant autodetachment signals arising from dipole bound states near the ground states of all three radicals were observed inmore »
- Authors:
-
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1469201
- Alternate Identifier(s):
- OSTI ID: 1465613
- Grant/Contract Number:
- SC0010326; CHE-0840494
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 149; Journal Issue: 7; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; quantum chemical dynamics; electron density; velocity map imaging; autoionization; oxides; photoelectron spectra; anion PE spectroscopy
Citation Formats
Kregel, Steven J., and Garand, Etienne. Ground and low-lying excited states of phenoxy, 1-naphthoxy, and 2-naphthoxy radicals via anion photoelectron spectroscopy. United States: N. p., 2018.
Web. doi:10.1063/1.5045685.
Kregel, Steven J., & Garand, Etienne. Ground and low-lying excited states of phenoxy, 1-naphthoxy, and 2-naphthoxy radicals via anion photoelectron spectroscopy. United States. https://doi.org/10.1063/1.5045685
Kregel, Steven J., and Garand, Etienne. Tue .
"Ground and low-lying excited states of phenoxy, 1-naphthoxy, and 2-naphthoxy radicals via anion photoelectron spectroscopy". United States. https://doi.org/10.1063/1.5045685. https://www.osti.gov/servlets/purl/1469201.
@article{osti_1469201,
title = {Ground and low-lying excited states of phenoxy, 1-naphthoxy, and 2-naphthoxy radicals via anion photoelectron spectroscopy},
author = {Kregel, Steven J. and Garand, Etienne},
abstractNote = {Here, we present the slow electron velocity map imaging spectroscopy of cryogenically cooled phenoxide, 1-naphthoxide, and 2-naphthoxide anions. The results allow us to examine the ground state and the lowest energy excited state in the corresponding neutral radicals. Care was taken to minimize autodetachment signals in the photoelectron spectra, allowing for more straightforward comparisons with Franck-Condon analyses. The ground states of these three aromatic oxide radicals all have the unpaired electron residing in a π orbital delocalized throughout the molecule. The electron affinity of 1-naphthoxy is measured to be 2.290(2) eV, while that of 2-naphthoxy is measured to be 2.404(2) eV, both of which are higher than that of the smaller phenoxy molecule at 2.253(1) eV. The first excited states have the unpaired electron residing in a more localized σ orbital, yielding measured term energies for the à state of 1.237(2) eV in 1-naphthoxy and 1.068(1) eV in 2-naphthoxy, while that of phenoxy is lower at 0.952(1) eV. The calculated Franck-Condon spectra generally showed good agreement with the experimental spectra, yielding assignments of the more active vibrations in each electronic state. Significant autodetachment signals arising from dipole bound states near the ground states of all three radicals were observed in our efforts to avoid them, and comparably less autodetachment signals were observed near the excited states. Besides this type of non-Franck-Condon intensities in the photoelectron spectra, we also observed minor features arising due to vibronic coupling in the ground states of all three radicals.},
doi = {10.1063/1.5045685},
journal = {Journal of Chemical Physics},
number = 7,
volume = 149,
place = {United States},
year = {Tue Aug 21 00:00:00 EDT 2018},
month = {Tue Aug 21 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Rapid Formation of Secondary Organic Aerosol from the Photolysis of 1-Nitronaphthalene: Role of Naphthoxy Radical Self-reaction
journal, October 2012
- Healy, Robert M.; Chen, Yang; Kourtchev, Ivan
- Environmental Science & Technology, Vol. 46, Issue 21
A multi-plate velocity-map imaging design for high-resolution photoelectron spectroscopy
journal, September 2017
- Kregel, Steven J.; Thurston, Glen K.; Zhou, Jia
- The Journal of Chemical Physics, Vol. 147, Issue 9
Ultrafast dynamics of formation and autodetachment of a dipole-bound state in an open-shell π-stacked dimer anion
journal, January 2016
- Bull, James N.; West, Christopher W.; Verlet, Jan R. R.
- Chemical Science, Vol. 7, Issue 8
Electronic states of the phenoxyl radical
journal, December 2001
- Radziszewski, J. George; Gil, Michal/; Gorski, Alexandr
- The Journal of Chemical Physics, Vol. 115, Issue 21
Infrared and Electronic Spectra of Radicals Produced from 2-Naphthol and Carbazole by UV-Induced Hydrogen-Atom Eliminations
journal, August 2012
- Sekine, Masahiko; Sekiya, Hiroshi; Nakata, Munetaka
- The Journal of Physical Chemistry A, Vol. 116, Issue 36
Slow photoelectron velocity-map imaging spectroscopy of the C 9 H 7 (indenyl) and C 13 H 9 (fluorenyl) anions
journal, September 2013
- Kim, Jongjin B.; Weichman, Marissa L.; Yacovitch, Tara I.
- The Journal of Chemical Physics, Vol. 139, Issue 10
How Accurate Are DFT Treatments of Organic Energies?
journal, May 2007
- Wodrich, Matthew D.; Corminboeuf, Clémence; Schreiner, Peter R.
- Organic Letters, Vol. 9, Issue 10
Vibrational state-selective autodetachment photoelectron spectroscopy from dipole-bound states of cold 2-hydroxyphenoxide: o − HO(C 6 H 4 )O −
journal, March 2015
- Huang, Dao-Ling; Liu, Hong-Tao; Ning, Chuan-Gang
- The Journal of Chemical Physics, Vol. 142, Issue 12
Anion resonances and above-threshold dynamics of coenzyme Q 0
journal, January 2015
- Bull, James N.; West, Christopher W.; Verlet, Jan R. R.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 24
On the Behavior of Cross Sections Near Thresholds
journal, May 1948
- Wigner, Eugene P.
- Physical Review, Vol. 73, Issue 9
Vibrations of the Phenoxyl Radical
journal, November 2001
- Spanget-Larsen, Jens; Gil, Michał; Gorski, Alexandr
- Journal of the American Chemical Society, Vol. 123, Issue 45
Theoretical Investigation of Molecular Properties of the First Excited State of the Phenoxyl Radical
journal, March 2008
- Cheng, Chi-Wen; Lee, Yuan-Pern; Witek, Henryk A.
- The Journal of Physical Chemistry A, Vol. 112, Issue 12
Observation of Mode-Specific Vibrational Autodetachment from Dipole-Bound States of Cold Anions
journal, July 2013
- Liu, Hong-Tao; Ning, Chuan-Gang; Huang, Dao-Ling
- Angewandte Chemie International Edition, Vol. 52, Issue 34
Laboratory Optical Spectroscopy of the Phenoxy Radical as a Candidate for Diffuse Interstellar Bands
journal, September 2015
- Araki, Mitsunori; Matsushita, Yuki; Tsukiyama, Koichi
- The Astronomical Journal, Vol. 150, Issue 4
The resonance Raman spectrum of phenoxyl radical
journal, July 1984
- Tripathi, G. N. R.; Schuler, Robert H.
- The Journal of Chemical Physics, Vol. 81, Issue 1
Ultraviolet photoelectron spectroscopy of the phenide, benzyl and phenoxide anions, with ab initio calculations
journal, September 1992
- Gunion, Robert F.; Gilles, Mary K.; Polak, Mark L.
- International Journal of Mass Spectrometry and Ion Processes, Vol. 117
Recursive methods for computing the Abel transform and its inverse
journal, January 1985
- Hansen, Eric W.; Law, Phaih-Lan
- Journal of the Optical Society of America A, Vol. 2, Issue 4
The electron spin resonance spectra of naphthoxyl radicals
journal, January 1973
- Dixon, William T.; Foster, Wendy E. J.; Murphy, David
- Journal of the Chemical Society, Perkin Transactions 2, Issue 15
Dynamics of π*-resonances in anionic clusters of para-toluquinone
journal, January 2017
- Bull, James N.; Verlet, Jan R. R.
- Phys. Chem. Chem. Phys., Vol. 19, Issue 39
Slow Electron Velocity-Map Imaging of Negative Ions: Applications to Spectroscopy and Dynamics †
journal, December 2008
- Neumark, Daniel M.
- The Journal of Physical Chemistry A, Vol. 112, Issue 51
Near-UV Absorption Spectrum of the Phenoxyl Radical and Kinetics of Its Reaction with CH 3 †
journal, September 2004
- Tonokura, Kenichi; Ogura, Teppei; Koshi, Mitsuo
- The Journal of Physical Chemistry A, Vol. 108, Issue 39
Magnetic-Bottle and velocity-map imaging photoelectron spectroscopy of APS − (A=C 14 H 10 or anthracene): Electron structure, spin-orbit coupling of APS • , and dipole-bound state of APS −
journal, August 2018
- Yuan, Qin-qin; Yang, Zheng; Li, Ren-zhong
- Chinese Journal of Chemical Physics, Vol. 31, Issue 4
A “circularisation” method to repair deformations and determine the centre of velocity map images
journal, July 2017
- Gascooke, Jason R.; Gibson, Stephen T.; Lawrance, Warren D.
- The Journal of Chemical Physics, Vol. 147, Issue 1
Spectroscopy and dynamics of the dipole‐bound state of acetaldehyde enolate
journal, December 1984
- Mead, Roy D.; Lykke, Keith R.; Lineberger, W. C.
- The Journal of Chemical Physics, Vol. 81, Issue 11
Rovibronic bands of the à B22←X̃ B21 transition of C6H5O and C6D5O detected with cavity ringdown absorption near 1.2 μm
journal, October 2008
- Cheng, Chi-Wen; Witek, Henryk; Lee, Yuan-Pern
- The Journal of Chemical Physics, Vol. 129, Issue 15
Slow photoelectron velocity-map imaging spectroscopy of the phenoxide and thiophenoxide anions
journal, January 2011
- Kim, Jongjin B.; Yacovitch, Tara I.; Hock, Christian
- Physical Chemistry Chemical Physics, Vol. 13, Issue 38
Atmospheric Chemistry of the Phenoxy Radical, C 6 H 5 O(•): UV Spectrum and Kinetics of Its Reaction with NO, NO 2 , and O 2
journal, October 1998
- Platz, J.; Nielsen, O. J.; Wallington, T. J.
- The Journal of Physical Chemistry A, Vol. 102, Issue 41
Ultraviolet Resonance Raman Spectroscopy and General Valence Force Field Analysis of Phenolate and Phenoxyl Radical
journal, April 1995
- Mukherjee, Arka; McGlashen, Michael L.; Spiro, Thomas G.
- The Journal of Physical Chemistry, Vol. 99, Issue 14
Observation of Mode-Specific Vibrational Autodetachment from Dipole-Bound States of Cold Anions
journal, July 2013
- Liu, Hong-Tao; Ning, Chuan-Gang; Huang, Dao-Ling
- Angewandte Chemie, Vol. 125, Issue 34
Works referencing / citing this record:
Fast beam photofragment translational spectroscopy of the phenoxy radical at 225 nm, 290 nm, and 533 nm
journal, January 2019
- Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 26
Photodetachment and photoreactions of substituted naphthalene anions in a tandem ion mobility spectrometer
journal, January 2019
- Bull, James N.; Buntine, Jack T.; Scholz, Michael S.
- Faraday Discussions, Vol. 217
Photodetachment of deprotonated aromatic amino acids: stability of the dehydrogenated radical depends on the deprotonation site
journal, January 2019
- Noble, Jennifer Anna; Aranguren-Abate, Juan P.; Dedonder, Claude
- Physical Chemistry Chemical Physics, Vol. 21, Issue 42
Photodetachment and Photoreactions of Substituted Naphthalene Anions in a Tandem Ion Mobility Spectrometer
text, January 2019
- Bull, James N.; Buntine, Jack T.; Scholz, Michael S.
- arXiv