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Title: Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl

Abstract

Spectroscopic constants (Te, re, B0, ωe, ωexe) have been calculated for the low-lying electronic states of UF, UF+, UCl, and UCl+ using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DK) Hamiltonians for the U atom. Spin orbit effects were included a posteri using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component (X2C) methods for U+ and UF+. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω=9/2 ground states. The first excited state of UCl was calculated to be an Ω=7/2 state at 78 cm-1 as opposed to the same state at 435 cm-1 in UF, andmore » the other low-lying states of UCl showed a similar compression relative to UF. Likewise UF+ and UCl+ both have Ω=4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states were energetically closer together in UCl+ than in UF+, ranging up to 776 cm-1 in UF+ and only 438 cm-1 in UCl+. As in previous research, the final PP-based SO-CASPT2 results for UF+ and UF agree well with experiment, and are expected to be predictive for UCl and UCl+, which are reported here for the first time.« less

Authors:
 [1]; ORCiD logo [1]
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  1. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1224465
Alternate Identifier(s):
OSTI ID: 1225988
Grant/Contract Number:  
SC0008501; FG02-12ER16329
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 18; 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; UF; UCl; uranium halides; uranium halide cations; ab initio; ground states; excitation energies; spin orbit interactions; electron correlation calculations; electron spectroscopy

Citation Formats

Bross, David H., and Peterson, Kirk A. Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl. United States: N. p., 2015. Web. doi:10.1063/1.4935492.
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Bross, David H., & Peterson, Kirk A. Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl. United States. https://doi.org/10.1063/1.4935492
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Bross, David H., and Peterson, Kirk A. Fri . "Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl". United States. https://doi.org/10.1063/1.4935492. https://www.osti.gov/servlets/purl/1224465.
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@article{osti_1224465,
title = {Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl},
author = {Bross, David H. and Peterson, Kirk A.},
abstractNote = {Spectroscopic constants (Te, re, B0, ωe, ωexe) have been calculated for the low-lying electronic states of UF, UF+, UCl, and UCl+ using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DK) Hamiltonians for the U atom. Spin orbit effects were included a posteri using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component (X2C) methods for U+ and UF+. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω=9/2 ground states. The first excited state of UCl was calculated to be an Ω=7/2 state at 78 cm-1 as opposed to the same state at 435 cm-1 in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise UF+ and UCl+ both have Ω=4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states were energetically closer together in UCl+ than in UF+, ranging up to 776 cm-1 in UF+ and only 438 cm-1 in UCl+. As in previous research, the final PP-based SO-CASPT2 results for UF+ and UF agree well with experiment, and are expected to be predictive for UCl and UCl+, which are reported here for the first time.},
doi = {10.1063/1.4935492},
journal = {Journal of Chemical Physics},
number = 18,
volume = 143,
place = {United States},
year = {Fri Nov 13 00:00:00 EST 2015},
month = {Fri Nov 13 00:00:00 EST 2015}
}
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    journal, August 2016

    • Lu, Qing; Peterson, Kirk A.
    • The Journal of Chemical Physics, Vol. 145, Issue 5
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    Spectroscopic and theoretical studies of ThCl and ThCl +
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    • VanGundy, Robert A.; Bartlett, Joshua H.; Heaven, Michael C.
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    • DOI: 10.1063/1.4975070
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