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Title: Experimental and Computational Description of the Interaction of H and H– with U

Abstract

In this work, the results of ab initio correlated molecular orbital theory electronic structure calculations for low-lying electronic states are presented for UH and UH– and compared to photoelectron spectroscopy measurements. The calculations were performed at the CCSD(T)/CBS and multireference CASPT2 including spin–orbit effects by the state interacting approach levels. The ground states of UH and UH– are predicted to be 4Ι9/2 and 5Λ6, respectively. The spectroscopic parameters Te, re, ωe, ωexe, and Be were obtained, and potential energy curves were calculated for the low energy Ω states of UH. The calculated adiabatic electron affinity is 0.468 eV in excellent agreement with an experimental value of 0.462 ± 0.013 eV. The lowest vertical detachment energy was predicted to be 0.506 eV for the ground state, and the adiabatic ionization energy (IE) is predicted to be 6.116 eV. The bond dissociation energy (BDE) and heat of formation values of UH were obtained using the IE calculated at the Feller–Peterson–Dixon level. For UH, UH–, and UH+, the BDEs were predicted to be 225.5, 197.9, and 235.5 kJ/mol, respectively. The BDE for UH is predicted to be ~20% lower in energy than that for ThH. The analysis of the natural bond orbitals showsmore » a significant U+H– ionic component in the bond of UH.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [2];  [2];  [2];  [2];  [2]; 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)
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1909831
Grant/Contract Number:  
SC0019317; SC0018921
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: 27; 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; Uranium

Citation Formats

de Melo, Gabriel F., Vasiliu, Monica, Marshall, Mary, Zhu, Zhaoguo, Tufekci, Burak A., Ciborowski, Sandra M., Blankenhorn, Moritz, Harris, Rachel M., Bowen, Kit H., and Dixon, David A. Experimental and Computational Description of the Interaction of H and H– with U. United States: N. p., 2022. Web. doi:10.1021/acs.jpca.2c03115.
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de Melo, Gabriel F., Vasiliu, Monica, Marshall, Mary, Zhu, Zhaoguo, Tufekci, Burak A., Ciborowski, Sandra M., Blankenhorn, Moritz, Harris, Rachel M., Bowen, Kit H., & Dixon, David A. Experimental and Computational Description of the Interaction of H and H– with U. United States. https://doi.org/10.1021/acs.jpca.2c03115
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de Melo, Gabriel F., Vasiliu, Monica, Marshall, Mary, Zhu, Zhaoguo, Tufekci, Burak A., Ciborowski, Sandra M., Blankenhorn, Moritz, Harris, Rachel M., Bowen, Kit H., and Dixon, David A. Wed . "Experimental and Computational Description of the Interaction of H and H– with U". United States. https://doi.org/10.1021/acs.jpca.2c03115. https://www.osti.gov/servlets/purl/1909831.
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@article{osti_1909831,
title = {Experimental and Computational Description of the Interaction of H and H– with U},
author = {de Melo, Gabriel F. and Vasiliu, Monica and Marshall, Mary and Zhu, Zhaoguo and Tufekci, Burak A. and Ciborowski, Sandra M. and Blankenhorn, Moritz and Harris, Rachel M. and Bowen, Kit H. and Dixon, David A.},
abstractNote = {In this work, the results of ab initio correlated molecular orbital theory electronic structure calculations for low-lying electronic states are presented for UH and UH– and compared to photoelectron spectroscopy measurements. The calculations were performed at the CCSD(T)/CBS and multireference CASPT2 including spin–orbit effects by the state interacting approach levels. The ground states of UH and UH– are predicted to be 4Ι9/2 and 5Λ6, respectively. The spectroscopic parameters Te, re, ωe, ωexe, and Be were obtained, and potential energy curves were calculated for the low energy Ω states of UH. The calculated adiabatic electron affinity is 0.468 eV in excellent agreement with an experimental value of 0.462 ± 0.013 eV. The lowest vertical detachment energy was predicted to be 0.506 eV for the ground state, and the adiabatic ionization energy (IE) is predicted to be 6.116 eV. The bond dissociation energy (BDE) and heat of formation values of UH were obtained using the IE calculated at the Feller–Peterson–Dixon level. For UH, UH–, and UH+, the BDEs were predicted to be 225.5, 197.9, and 235.5 kJ/mol, respectively. The BDE for UH is predicted to be ~20% lower in energy than that for ThH. The analysis of the natural bond orbitals shows a significant U+H– ionic component in the bond of UH.},
doi = {10.1021/acs.jpca.2c03115},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 27,
volume = 126,
place = {United States},
year = {Wed Jun 29 00:00:00 EDT 2022},
month = {Wed Jun 29 00:00:00 EDT 2022}
}
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