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Title: 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 » 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.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. 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) (SC-22); 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. doi: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. doi: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 = {2018},
month = {8}
}

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