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Title: Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/–

Abstract

A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC–, and UC+ molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller–Peterson–Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC– and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN+, the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC0/+/– molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidationmore » state of the U atom in terms of the 7s orbital occupation: UC (5f27s1), UC– (5f27s2), and UC+ (5f27s0). Furthermore, the behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.« less

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:
1909836
Grant/Contract Number:  
SC0019317; SC0018921; 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: 50; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Basis sets; Chemical calculations; Electrical energy; Luminescence; Potential energy

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. Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/–. United States: N. p., 2022. Web. doi:10.1021/acs.jpca.2c06978.
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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. Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/–. United States. https://doi.org/10.1021/acs.jpca.2c06978
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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. Mon . "Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/–". United States. https://doi.org/10.1021/acs.jpca.2c06978. https://www.osti.gov/servlets/purl/1909836.
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@article{osti_1909836,
title = {Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/–},
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 = {A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC–, and UC+ molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller–Peterson–Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC– and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN+, the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC0/+/– molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidation state of the U atom in terms of the 7s orbital occupation: UC (5f27s1), UC– (5f27s2), and UC+ (5f27s0). Furthermore, the behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.},
doi = {10.1021/acs.jpca.2c06978},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 50,
volume = 126,
place = {United States},
year = {Mon Dec 12 00:00:00 EST 2022},
month = {Mon Dec 12 00:00:00 EST 2022}
}
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