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Title: Spectroscopic and theoretical studies of UN and UN +

Abstract

The low energy electronic states of UN and UN+ have been examined using high-level electronic structure calculations and two-color photoionization techniques. The experimental measurements provided an accurate ionization energy for UN (IE=50802±5 cm-1). Spectra for UN+ yielded ro-vibrational constants and established that the ground state has the electronic angular momentum projection Ω=4. Ab initio calculations were carried out using the spin-orbit state interacting approach with the complete active space 2nd-order perturbation theory (CASPT2) method. A series of correlation consistent basis sets were used in conjunction with small-core relativistic pseudopotentials on U to extrapolate to the complete basis set (CBS) limits. The results for UN correctly obtained an Ω=3.5 ground state and demonstrated a high density of configurationally related excited states with closely similar ro-vibrational constants. Similar results were obtained for UN+, with reduced complexity owing to the smaller number of outer-shell electrons. The calculated IE for UN was in excellent agreement with the measured value. Improved values for the dissociation energies of UN and UN+, as well as their heats of formation, were obtained using the Feller-Peterson-Dixon composite thermochemistry method including corrections up through CCSDTQ. An analysis of the ab initio results from the perspective of ligand field theory showsmore » that the patterns of electronic states for both UN and UN+ can be understood in terms of the underlying energy level structure of the atomic metal ion.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [3]; ORCiD logo [3]
  1. Washington State Univ., Pullman, WA (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Emory Univ., Atlanta, GA (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1632833
Alternate Identifier(s):
OSTI ID: 1602343; OSTI ID: 1773730
Grant/Contract Number:  
AC02-06CH11357; SC0008501; FG02-01ER15153
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 9; 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; Spectroscopy; Theoretical Chemistry

Citation Formats

Battey, S. R., Bross, D. H., Peterson, K. A., Persinger, T. D., VanGundy, R. A., and Heaven, M. C.. Spectroscopic and theoretical studies of UN and UN +. United States: N. p., 2020. Web. https://doi.org/10.1063/1.5144299.
Battey, S. R., Bross, D. H., Peterson, K. A., Persinger, T. D., VanGundy, R. A., & Heaven, M. C.. Spectroscopic and theoretical studies of UN and UN +. United States. https://doi.org/10.1063/1.5144299
Battey, S. R., Bross, D. H., Peterson, K. A., Persinger, T. D., VanGundy, R. A., and Heaven, M. C.. Sat . "Spectroscopic and theoretical studies of UN and UN +". United States. https://doi.org/10.1063/1.5144299. https://www.osti.gov/servlets/purl/1632833.
@article{osti_1632833,
title = {Spectroscopic and theoretical studies of UN and UN +},
author = {Battey, S. R. and Bross, D. H. and Peterson, K. A. and Persinger, T. D. and VanGundy, R. A. and Heaven, M. C.},
abstractNote = {The low energy electronic states of UN and UN+ have been examined using high-level electronic structure calculations and two-color photoionization techniques. The experimental measurements provided an accurate ionization energy for UN (IE=50802±5 cm-1). Spectra for UN+ yielded ro-vibrational constants and established that the ground state has the electronic angular momentum projection Ω=4. Ab initio calculations were carried out using the spin-orbit state interacting approach with the complete active space 2nd-order perturbation theory (CASPT2) method. A series of correlation consistent basis sets were used in conjunction with small-core relativistic pseudopotentials on U to extrapolate to the complete basis set (CBS) limits. The results for UN correctly obtained an Ω=3.5 ground state and demonstrated a high density of configurationally related excited states with closely similar ro-vibrational constants. Similar results were obtained for UN+, with reduced complexity owing to the smaller number of outer-shell electrons. The calculated IE for UN was in excellent agreement with the measured value. Improved values for the dissociation energies of UN and UN+, as well as their heats of formation, were obtained using the Feller-Peterson-Dixon composite thermochemistry method including corrections up through CCSDTQ. An analysis of the ab initio results from the perspective of ligand field theory shows that the patterns of electronic states for both UN and UN+ can be understood in terms of the underlying energy level structure of the atomic metal ion.},
doi = {10.1063/1.5144299},
journal = {Journal of Chemical Physics},
number = 9,
volume = 152,
place = {United States},
year = {2020},
month = {3}
}

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