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Title: Electronic Properties of UN and UN– from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory

Abstract

In this work, the results of calculations of the properties of the anion UN– including electron detachment are described, which further expand our knowledge of this diatomic molecule. High-level electronic structure calculations were conducted for the UN and UN– diatomic molecules and compared to photoelectron spectroscopy measurements. The low-lying Ω states were obtained using multireference CASPT2 including spin-orbit effects up to ~20,000 cm–1 . At the Feller–Peterson–Dixon (FPD) level, the adiabatic electron affinity (AEA) of UN is estimated to be 1.402 eV and the vertical detachment energy (VDE) is 1.423 eV. The assignment of the UN excited states shows good agreement with the experimental results with a VDE of 1.424 eV. An Ω = 4 ground state was obtained for UN– which is mainly associated with the 3H ΛS state. Thermochemical calculations estimate a bond dissociation energy (BDE) for UN– (U– + N) of 665.9 kJ/mol, ~15% larger than that of UN and UN+. The NBO analysis reveals U–N triple bonds for the UN, UN–, and UN+ species.

Authors:
 [1];  [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2];  [2];  [2];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Alabama, Tuscaloosa, AL (United States)
  2. Johns Hopkins Univ., Baltimore, MD (United States)
  3. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1909832
Grant/Contract Number:  
SC0019317; SC0008501
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 126; Journal Issue: 43; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; Basis sets; Chemical calculations; Electrical energy; Quantum mechanics

Citation Formats

de Melo, Gabriel F., Vasiliu, Monica, Liu, Gaoxiang, Ciborowski, Sandra, Zhu, Zhaoguo, Blankenhorn, Moritz, Harris, Rachel, Martinez-Martinez, Chalynette, Dipalo, Maria, Peterson, Kirk A., Bowen, Kit H., and Dixon, David A. Electronic Properties of UN and UN– from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory. United States: N. p., 2022. Web. doi:10.1021/acs.jpca.2c06012.
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de Melo, Gabriel F., Vasiliu, Monica, Liu, Gaoxiang, Ciborowski, Sandra, Zhu, Zhaoguo, Blankenhorn, Moritz, Harris, Rachel, Martinez-Martinez, Chalynette, Dipalo, Maria, Peterson, Kirk A., Bowen, Kit H., & Dixon, David A. Electronic Properties of UN and UN– from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory. United States. https://doi.org/10.1021/acs.jpca.2c06012
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de Melo, Gabriel F., Vasiliu, Monica, Liu, Gaoxiang, Ciborowski, Sandra, Zhu, Zhaoguo, Blankenhorn, Moritz, Harris, Rachel, Martinez-Martinez, Chalynette, Dipalo, Maria, Peterson, Kirk A., Bowen, Kit H., and Dixon, David A. Fri . "Electronic Properties of UN and UN– from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory". United States. https://doi.org/10.1021/acs.jpca.2c06012. https://www.osti.gov/servlets/purl/1909832.
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@article{osti_1909832,
title = {Electronic Properties of UN and UN– from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory},
author = {de Melo, Gabriel F. and Vasiliu, Monica and Liu, Gaoxiang and Ciborowski, Sandra and Zhu, Zhaoguo and Blankenhorn, Moritz and Harris, Rachel and Martinez-Martinez, Chalynette and Dipalo, Maria and Peterson, Kirk A. and Bowen, Kit H. and Dixon, David A.},
abstractNote = {In this work, the results of calculations of the properties of the anion UN– including electron detachment are described, which further expand our knowledge of this diatomic molecule. High-level electronic structure calculations were conducted for the UN and UN– diatomic molecules and compared to photoelectron spectroscopy measurements. The low-lying Ω states were obtained using multireference CASPT2 including spin-orbit effects up to ~20,000 cm–1 . At the Feller–Peterson–Dixon (FPD) level, the adiabatic electron affinity (AEA) of UN is estimated to be 1.402 eV and the vertical detachment energy (VDE) is 1.423 eV. The assignment of the UN excited states shows good agreement with the experimental results with a VDE of 1.424 eV. An Ω = 4 ground state was obtained for UN– which is mainly associated with the 3H ΛS state. Thermochemical calculations estimate a bond dissociation energy (BDE) for UN– (U– + N) of 665.9 kJ/mol, ~15% larger than that of UN and UN+. The NBO analysis reveals U–N triple bonds for the UN, UN–, and UN+ species.},
doi = {10.1021/acs.jpca.2c06012},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 43,
volume = 126,
place = {United States},
year = {Fri Oct 21 00:00:00 EDT 2022},
month = {Fri Oct 21 00:00:00 EDT 2022}
}
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