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Title: One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure

Abstract

Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73 570 ± 6 cm{sup −1} (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ({sup 2}A{sub 2}), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded thatmore » upon ionization the pyridine cation in the ground electronic state should have a planar structure of C{sub 2v} symmetry through the C-N axis.« less

Authors:
;
Publication Date:
OSTI Identifier:
22310781
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 17; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATIONS; EFFICIENCY; GROUND STATES; PEAKS; PHOTOELECTRON SPECTROSCOPY; PHOTOIONIZATION; PHOTONS; PYRIDINE; SPECTRA

Citation Formats

Lee, Yu Ran, Kang, Do Won, Kim, Hong Lae, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr, and Kwon, Chan Ho, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr. One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure. United States: N. p., 2014. Web. doi:10.1063/1.4900569.
Lee, Yu Ran, Kang, Do Won, Kim, Hong Lae, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr, & Kwon, Chan Ho, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr. One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure. United States. https://doi.org/10.1063/1.4900569
Lee, Yu Ran, Kang, Do Won, Kim, Hong Lae, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr, and Kwon, Chan Ho, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr. 2014. "One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure". United States. https://doi.org/10.1063/1.4900569.
@article{osti_22310781,
title = {One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure},
author = {Lee, Yu Ran and Kang, Do Won and Kim, Hong Lae, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr and Kwon, Chan Ho, E-mail: chkwon@kangwon.ac.kr, E-mail: hlkim@kangwon.ac.kr},
abstractNote = {Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73 570 ± 6 cm{sup −1} (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ({sup 2}A{sub 2}), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded that upon ionization the pyridine cation in the ground electronic state should have a planar structure of C{sub 2v} symmetry through the C-N axis.},
doi = {10.1063/1.4900569},
url = {https://www.osti.gov/biblio/22310781}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 141,
place = {United States},
year = {Fri Nov 07 00:00:00 EST 2014},
month = {Fri Nov 07 00:00:00 EST 2014}
}