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Title: Photoelectron spectroscopy of anthracene and fluoranthene radical anions

Abstract

Here, we report the slow electron velocity map imaging spectroscopy of cryogenically cooled anthracene and fluoranthene radical anions, two similarly sized polycyclic aromatic hydrocarbon molecules. The results allow us to examine the lowest energy singlet and triplet states in the neutral molecules on equal footing from the anionic ground state. The analysis of the experimental spectra is aided by harmonic calculations and Franck-Condon simulations, which generally show good agreement with experimental values and spectra. The electron affinity of fluoranthene is measured to be 0.757(2) eV, which is larger than that of anthracene at 0.532(3) eV. The lowest energy triplet state in anthracene is observed at 1.872(3) eV above the singlet ground state, while that of fluoranthene is observed at 2.321(2) eV above its singlet ground state. Comparisons of experimental and calculated spectra show that in addition to the Franck-Condon active modes, there is a clear presence of vibrational modes that gain intensity via vibronic coupling in both the singlet and triplet states in both molecules. In addition, the triplet state generally exhibits increased vibronic coupling compared to the singlet state, with the fluoranthene triplet state exhibiting evidence of distortion from C2v symmetry.

Authors:
ORCiD logo [1]; 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); National Science Foundation (NSF)
OSTI Identifier:
1469198
Alternate Identifier(s):
OSTI ID: 1456264
Grant/Contract Number:  
SC0010326; CHE-0840494
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 23; 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; ion-trap; velocity map imaging; organic compounds; gas phase; Karlsruhe basis sets; photoelectron spectroscopy; triplet state

Citation Formats

Kregel, Steven J., Thurston, Glen K., and Garand, Etienne. Photoelectron spectroscopy of anthracene and fluoranthene radical anions. United States: N. p., 2018. Web. doi:10.1063/1.5036757.
Kregel, Steven J., Thurston, Glen K., & Garand, Etienne. Photoelectron spectroscopy of anthracene and fluoranthene radical anions. United States. doi:10.1063/1.5036757.
Kregel, Steven J., Thurston, Glen K., and Garand, Etienne. Thu . "Photoelectron spectroscopy of anthracene and fluoranthene radical anions". United States. doi:10.1063/1.5036757. https://www.osti.gov/servlets/purl/1469198.
@article{osti_1469198,
title = {Photoelectron spectroscopy of anthracene and fluoranthene radical anions},
author = {Kregel, Steven J. and Thurston, Glen K. and Garand, Etienne},
abstractNote = {Here, we report the slow electron velocity map imaging spectroscopy of cryogenically cooled anthracene and fluoranthene radical anions, two similarly sized polycyclic aromatic hydrocarbon molecules. The results allow us to examine the lowest energy singlet and triplet states in the neutral molecules on equal footing from the anionic ground state. The analysis of the experimental spectra is aided by harmonic calculations and Franck-Condon simulations, which generally show good agreement with experimental values and spectra. The electron affinity of fluoranthene is measured to be 0.757(2) eV, which is larger than that of anthracene at 0.532(3) eV. The lowest energy triplet state in anthracene is observed at 1.872(3) eV above the singlet ground state, while that of fluoranthene is observed at 2.321(2) eV above its singlet ground state. Comparisons of experimental and calculated spectra show that in addition to the Franck-Condon active modes, there is a clear presence of vibrational modes that gain intensity via vibronic coupling in both the singlet and triplet states in both molecules. In addition, the triplet state generally exhibits increased vibronic coupling compared to the singlet state, with the fluoranthene triplet state exhibiting evidence of distortion from C2v symmetry.},
doi = {10.1063/1.5036757},
journal = {Journal of Chemical Physics},
number = 23,
volume = 148,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: Structure of anthracene (left) and fluoranthene (right) along with the SOMO and HOMO-1 of their respective anion.

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    Works referencing / citing this record:

    Vibrationally resolved photoelectron spectroscopy of oligothiophene radical anions
    journal, October 2019

    • Thurston, Glen K.; Sagan, Cole R.; Garand, Etienne
    • The Journal of Chemical Physics, Vol. 151, Issue 16
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.