Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions

Logan J. Augustine; Mikaela Mary F. Pyrch; Dmytro V. Kravchuk; Jay M. Williams; Sara E. Mason; Tori Z. Forbes

doi:10.1002/ejic.202200693

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Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions

Journal article

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Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions

Logan J. Augustine, Mikaela Mary F. Pyrch, Dmytro V. Kravchuk, Jay M. Williams, Sara E. Mason and Tori Z. Forbes

European journal of inorganic chemistry, Vol.26(14), e202200693

05/12/2023

DOI: 10.1002/ejic.202200693

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Abstract

Actinyl-actinyl interactions are particularly prevalent for the pentavalent neptunyl cation (Np(V)O2)+ where these interactions appear either as a T- or D-shape (diamond-shape). T-shaped interactions have been previously identified in high concentration Np(V) solutions containing simple anions (NO3−, ClO4−, Cl−) whereas D-shaped have only been isolated in the solid-state in the presence of carboxylate ligands. In this study, Density Functional Theory (DFT) calculations were paired with Raman spectroscopy to evaluate the formation of D-shaped interactions in the presence of aliphatic (R=H (formate), CH3 (acetate), CH2CH3 (propionate)) and aromatic (R=C6H5 (benzoate), C6H4OH (4-hydroxybenzoate), C5H4N (isonicotinate)) carboxylate ligands. DFT studies indicate that the ΔG to form hydrated T- and D-shaped forms are not spontaneous but become so with the addition of the carboxylate ligands. Raman spectra of the Np(V) carboxylate solutions contained vibrational modes associated with the D-shaped interactions, but spectral changes observed over time indicate a dynamic system. Crystallization experiments from the Np(V) carboxylate systems confirmed the presence of D-shaped dimers for the aromatic carboxylates, suggesting that the choice of the anion in solution favors actinyl-actinyl interactions even at low concentrations (≤20 mM) of Np(V)

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actinyl-actinyl interaction

CCI

density functional calculations

neptunium

raman spectroscopy

Details

Title: Subtitle: Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions
Creators: Logan J. Augustine - University of Iowa
Mikaela Mary F. Pyrch - University of Iowa
Dmytro V. Kravchuk - University of Iowa
Jay M. Williams - University of Iowa
Sara E. Mason - University of Iowa
Tori Z. Forbes - University of Iowa
Resource Type: Journal article
Publication Details: European journal of inorganic chemistry, Vol.26(14), e202200693
DOI: 10.1002/ejic.202200693
ISSN: 1434-1948
eISSN: 1099-0682
Publisher: Wiley
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-SC0021420
Language: English
Electronic publication date: 03/22/2023
Date published: 05/12/2023
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984385053902771

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