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Title: Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states

Abstract

We report a photodetachment spectroscopy and high-resolution resonant photoelectron imaging study of cryogenically-cooled 2-naphthoxide anions (C10H7O-). The photodetachment spectrum revealed a dipole-bound state (DBS) 202(4) cm-1 below the detachment threshold and thirty-eight resonances corresponding to the vibrational levels of the DBS. By tuning the detachment laser to these above-threshold resonances, we obtained thirty-eight resonantly-enhanced photoelectron spectra, which were highly non-Franck-Condon as a result of mode-selective vibrational auto-detachment from the DBS. The resonances were assigned by comparing the resonant and non-resonant photoelectron spectra, assisted by the computed vibrational frequencies. Specifically, vibrational features with low Franck-Condon factors or from Franck-Condon-forbidden vibrational modes were significantly enhanced in the resonant photoelectron spectra, resulting in much richer spectroscopic information. The electron affinity of the 2-naphthoxy radical was measured accurately to be 19,387(4) cm-1 or 2.4037(5) eV. In addition, a total of seventeen vibrational frequencies were obtained for the 2-naphthoxy radical. In particular, seven Franck-Condon-forbidden out-of-plane bending modes, including the two lowest frequency modes (ν48 at 102 cm-1 and ν47 at 171 cm-1), were observed, demonstrating the advantages of combining photodetachment spectroscopy and resonant photoelectron spectroscopy in obtaining vibrational information for polar radical species via DBS.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Brown Univ., Providence, RI (United States). Dept. of Chemistry
  2. Brown Univ., Providence, RI (United States). Dept. of Chemistry; Univ. of California, Los Angeles, CA (United States). Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1775300
Alternate Identifier(s):
OSTI ID: 1632041
Grant/Contract Number:  
SC0018679
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 21; 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

Citation Formats

Qian, Chen-Hui, Zhu, Guo-Zhu, Zhang, Yue-Rou, and Wang, Lai-Sheng. Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states. United States: N. p., 2020. Web. doi:10.1063/5.0011234.
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Qian, Chen-Hui, Zhu, Guo-Zhu, Zhang, Yue-Rou, & Wang, Lai-Sheng. Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states. United States. https://doi.org/10.1063/5.0011234
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Qian, Chen-Hui, Zhu, Guo-Zhu, Zhang, Yue-Rou, and Wang, Lai-Sheng. Fri . "Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states". United States. https://doi.org/10.1063/5.0011234. https://www.osti.gov/servlets/purl/1775300.
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@article{osti_1775300,
title = {Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states},
author = {Qian, Chen-Hui and Zhu, Guo-Zhu and Zhang, Yue-Rou and Wang, Lai-Sheng},
abstractNote = {We report a photodetachment spectroscopy and high-resolution resonant photoelectron imaging study of cryogenically-cooled 2-naphthoxide anions (C10H7O-). The photodetachment spectrum revealed a dipole-bound state (DBS) 202(4) cm-1 below the detachment threshold and thirty-eight resonances corresponding to the vibrational levels of the DBS. By tuning the detachment laser to these above-threshold resonances, we obtained thirty-eight resonantly-enhanced photoelectron spectra, which were highly non-Franck-Condon as a result of mode-selective vibrational auto-detachment from the DBS. The resonances were assigned by comparing the resonant and non-resonant photoelectron spectra, assisted by the computed vibrational frequencies. Specifically, vibrational features with low Franck-Condon factors or from Franck-Condon-forbidden vibrational modes were significantly enhanced in the resonant photoelectron spectra, resulting in much richer spectroscopic information. The electron affinity of the 2-naphthoxy radical was measured accurately to be 19,387(4) cm-1 or 2.4037(5) eV. In addition, a total of seventeen vibrational frequencies were obtained for the 2-naphthoxy radical. In particular, seven Franck-Condon-forbidden out-of-plane bending modes, including the two lowest frequency modes (ν48 at 102 cm-1 and ν47 at 171 cm-1), were observed, demonstrating the advantages of combining photodetachment spectroscopy and resonant photoelectron spectroscopy in obtaining vibrational information for polar radical species via DBS.},
doi = {10.1063/5.0011234},
journal = {Journal of Chemical Physics},
number = 21,
volume = 152,
place = {United States},
year = {Fri Jun 05 00:00:00 EDT 2020},
month = {Fri Jun 05 00:00:00 EDT 2020}
}
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