Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl-Cation and Uranyl-Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

Logan J Augustine; Harindu Rajapaksha; Mikaela Mary F Pyrch; Maguire Kasperski; Tori Z Forbes; Sara E Mason

doi:10.1021/acs.inorgchem.2c03476

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Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl-Cation and Uranyl-Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

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Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl-Cation and Uranyl-Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

Logan J Augustine, Harindu Rajapaksha, Mikaela Mary F Pyrch, Maguire Kasperski, Tori Z Forbes and Sara E Mason

Inorganic chemistry, Vol.62(1), pp.372-380

01/09/2023

DOI: 10.1021/acs.inorgchem.2c03476

PMCID: PMC9832540

PMID: 36538814

Appears in UI Libraries Support Open Access

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Abstract

Solid-state uranyl hybrid structures are often formed through unique intermolecular interactions occurring between a molecular uranyl anion and a charge-balancing cation. In this work, solid-state structures of the uranyl tetrachloride anion engaged in uranyl-cation and uranyl-hydrogen interactions were studied using density functional theory (DFT). As most first-principles methods used for systems of this type focus primarily on the molecular structure, we present an extensive benchmarking study to understand the methods needed to accurately model the geometric properties of these systems. From there, the electronic and vibrational structures of the compounds were investigated through projected density of states and phonon analysis and compared to the experiment. Lastly, we present a DFT + thermodynamics approach to calculate the formation enthalpies (Δ ) of these systems to directly relate to experimental values. Through this methodology, we were able to accurately capture trends observed in experimental results and saw good quantitative agreement in predicted Δ compared to the value calculated through referencing each structure to its standard state. Overall, results from this work will be used for future combined experimental and computational studies on both uranyl and neptunyl hybrid structures to delineate how varying intermolecular interaction strengths relates to the overall values of Δ .

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Title: Subtitle: Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl-Cation and Uranyl-Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses
Creators: Logan J Augustine - Department of Chemistry, University of Iowa, Iowa City, Iowa52242, United States
Harindu Rajapaksha - Department of Chemistry, University of Iowa, Iowa City, Iowa52242, United States
Mikaela Mary F Pyrch - University of Iowa
Maguire Kasperski - Department of Chemistry, University of Iowa, Iowa City, Iowa52242, United States
Tori Z Forbes - University of Iowa
Sara E Mason - University of Iowa
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.62(1), pp.372-380
DOI: 10.1021/acs.inorgchem.2c03476
PMID: 36538814
PMCID: PMC9832540
NLM abbreviation: Inorg Chem
ISSN: 0020-1669
eISSN: 1520-510X
Publisher: American Chemical Society
Grant note: DOI: 10.13039/100006132, name: Office of Science, award: DE-SC0021420; DOI: 10.13039/100006231, name: Brookhaven National Laboratory, award: DE-SC0012704
Language: English
Electronic publication date: 12/20/2022
Date published: 01/09/2023
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984339358702771

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