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Title: Spectroscopic and theoretical studies of ThCl and ThCl+

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.4975070 · OSTI ID:1465687
 [1];  [2];  [2];  [3]; ORCiD logo [3]
  1. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry; Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA
  2. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
  3. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
+ Show Author Affiliations

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-, X2 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- X3 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.

Research Organization:
Emory Univ., Atlanta, GA (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-01ER15153; SC0008501
OSTI ID:
1465687
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 146; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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