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Title: Spectroscopic and theoretical studies of ThCl and ThCl+

Abstract

In this paper, the electronic structures of ThCl and ThCl+ have been examined using laser induced fluorescence and two-photon ionization techniques. Rotationally resolved spectra, combined with the predictions from relativistic electronic structure calculations, show that the ground state of the neutral molecule is Th+(7s26d)Cl-, X 2 Δ 3 / 2 . Dispersed fluorescence spectra for ThCl revealed the ground state vibrational levels v = 0-10 and low energy electronic states that also originate from the atomic ion 7s26d configuration. Pulsed field ionization—zero kinetic energy photoelectron spectroscopy established an ionization energy (IE) for ThCl of 51 344(5) cm-1, and the ThCl+ vibrational term energies of the v = 1-3 levels. The zero-point level of the first electronically excited state was found at 949(2) cm-1. Comparisons with high-level theoretical results indicate that the ground and excited states are Th2+(7s6d)Cl- X 3 Δ 1 and Th2+(7s2)Cl- Σ + 1 , respectively. Finally, relativistic coupled cluster composite thermochemistry calculations yielded an IE within 1.2 kcal/mol of experiment and a bond dissociation energy (118.3 kcal/mol) in perfect agreement with previous experiments.

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [2]
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  1. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
  2. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465687
Alternate Identifier(s):
OSTI ID: 1361762
Grant/Contract Number:  
FG02-01ER15153; FG02-12ER16329
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 5; 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; ionization; excited states; basis sets; laser induced fluorescence; electron spectroscopy; ligand fields; ground states; display devices; dissociation energies; fluorescence spectra

Citation Formats

VanGundy, Robert A., Bartlett, Joshua H., Heaven, Michael C., Battey, Samuel R., and Peterson, Kirk A. Spectroscopic and theoretical studies of ThCl and ThCl+. United States: N. p., 2017. Web. doi:10.1063/1.4975070.
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VanGundy, Robert A., Bartlett, Joshua H., Heaven, Michael C., Battey, Samuel R., & Peterson, Kirk A. Spectroscopic and theoretical studies of ThCl and ThCl+. United States. doi:10.1063/1.4975070.
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VanGundy, Robert A., Bartlett, Joshua H., Heaven, Michael C., Battey, Samuel R., and Peterson, Kirk A. Tue . "Spectroscopic and theoretical studies of ThCl and ThCl+". United States. doi:10.1063/1.4975070. https://www.osti.gov/servlets/purl/1465687.
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@article{osti_1465687,
title = {Spectroscopic and theoretical studies of ThCl and ThCl+},
author = {VanGundy, Robert A. and Bartlett, Joshua H. and Heaven, Michael C. and Battey, Samuel R. and Peterson, Kirk A.},
abstractNote = {In this paper, the electronic structures of ThCl and ThCl+ have been examined using laser induced fluorescence and two-photon ionization techniques. Rotationally resolved spectra, combined with the predictions from relativistic electronic structure calculations, show that the ground state of the neutral molecule is Th+(7s26d)Cl-, X2Δ3/2. Dispersed fluorescence spectra for ThCl revealed the ground state vibrational levels v = 0-10 and low energy electronic states that also originate from the atomic ion 7s26d configuration. Pulsed field ionization—zero kinetic energy photoelectron spectroscopy established an ionization energy (IE) for ThCl of 51 344(5) cm-1, and the ThCl+ vibrational term energies of the v = 1-3 levels. The zero-point level of the first electronically excited state was found at 949(2) cm-1. Comparisons with high-level theoretical results indicate that the ground and excited states are Th2+(7s6d)Cl- X3Δ1 and Th2+(7s2)Cl- Σ+1, respectively. Finally, relativistic coupled cluster composite thermochemistry calculations yielded an IE within 1.2 kcal/mol of experiment and a bond dissociation energy (118.3 kcal/mol) in perfect agreement with previous experiments.},
doi = {10.1063/1.4975070},
journal = {Journal of Chemical Physics},
number = 5,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}
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DOI:  10.1063/1.4975070
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