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Ground and low-lying excited states of phenoxy, 1-naphthoxy, and 2-naphthoxy radicals via anion photoelectron spectroscopy

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5045685· OSTI ID:1469201
 [1];  [2]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry; University of Wisconsin-Madison Department of Chemistry
  2. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
+ Show Author Affiliations
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.
Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0010326
OSTI ID:
1469201
Alternate ID(s):
OSTI ID: 1465613
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 149; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Fast beam photofragment translational spectroscopy of the phenoxy radical at 225 nm, 290 nm, and 533 nm journal January 2019
Photodetachment and photoreactions of substituted naphthalene anions in a tandem ion mobility spectrometer journal January 2019
Photodetachment of deprotonated aromatic amino acids: stability of the dehydrogenated radical depends on the deprotonation site journal January 2019
Photodetachment and Photoreactions of Substituted Naphthalene Anions in a Tandem Ion Mobility Spectrometer text January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anion PE spectroscopy
autoionization
electron density
oxides
photoelectron spectra
quantum chemical dynamics
velocity map imaging