Structure and stability of aquotetrafluorouranyl(VI) in the solid state - Density functional study of [UO2F4(H2O)][NMe4]2·2H2O1,2

Michael Buehl

doi:10.1139/V08-182

Structure and stability of aquotetrafluorouranyl(VI) in the solid state - Density functional study of [UO₂F₄(H₂O)][NMe₄]₂·2H₂O^1,2

Michael Buehl

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8 Citations (Scopus)

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Abstract

Periodic density functional computations have been performed for solid [UO₂F₄(H₂O)][NMe₄]₂·2H(₂)O at the BLYP level. A model with disordered fluoro and aquo ligands in the uranyl anion is significantly lower in energy than one with a symmetrical assignment of these sites, which was favored in the original X-ray crystallography study. According to optimized energies and Car-Parrinello molecular dynamics (CPMD) simulations, the [UO₂F₄(H₂O)]^2- ion in the solid is stable with respect to loss of the coordinated water molecule. In contrast, CPMD simulations had found this ligand to be unbound in aqueous solution. The role of the counterions in stabilizing the higher coordination number in the crystal is discussed.

Original language	English
Pages (from-to)	818-823
Number of pages	6
Journal	Canadian Journal of Chemistry
Volume	87
Issue number	7
DOIs	https://doi.org/10.1139/V08-182
Publication status	Published - Jul 2009

Keywords

Uranyl complexes
Density functional computations
Molecular dynamics
Simulations
Counterion effects
Initio molecular-dynamics
Water-exchange mechanism
Aqueous uranyl(vi) ion
AB-initio
Practical tool
Complexes
Energy
Pseudopotentials
Energetics

Access to Document

10.1139/V08-182

CPMD study of solid [NMe4]2[UO2F4(H2O)]
This is the author's revised version after peer review. Published version of this article (c) NRC Research Press is available from DOI: 10.1139/V08-182
Accepted author manuscript, 368 KB

Cite this

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title = "Structure and stability of aquotetrafluorouranyl(VI) in the solid state - Density functional study of [UO2F4(H2O)][NMe4]2·2H2O1,2",

abstract = "Periodic density functional computations have been performed for solid [UO2F4(H2O)][NMe4]2·2H(2)O at the BLYP level. A model with disordered fluoro and aquo ligands in the uranyl anion is significantly lower in energy than one with a symmetrical assignment of these sites, which was favored in the original X-ray crystallography study. According to optimized energies and Car-Parrinello molecular dynamics (CPMD) simulations, the [UO2F4(H2O)]2- ion in the solid is stable with respect to loss of the coordinated water molecule. In contrast, CPMD simulations had found this ligand to be unbound in aqueous solution. The role of the counterions in stabilizing the higher coordination number in the crystal is discussed.",

keywords = "Uranyl complexes, Density functional computations, Molecular dynamics, Simulations, Counterion effects, Initio molecular-dynamics, Water-exchange mechanism, Aqueous uranyl(vi) ion, AB-initio, Practical tool, Complexes, Energy, Pseudopotentials, Energetics",

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year = "2009",

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AB - Periodic density functional computations have been performed for solid [UO2F4(H2O)][NMe4]2·2H(2)O at the BLYP level. A model with disordered fluoro and aquo ligands in the uranyl anion is significantly lower in energy than one with a symmetrical assignment of these sites, which was favored in the original X-ray crystallography study. According to optimized energies and Car-Parrinello molecular dynamics (CPMD) simulations, the [UO2F4(H2O)]2- ion in the solid is stable with respect to loss of the coordinated water molecule. In contrast, CPMD simulations had found this ligand to be unbound in aqueous solution. The role of the counterions in stabilizing the higher coordination number in the crystal is discussed.

KW - Uranyl complexes

KW - Density functional computations

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KW - Simulations

KW - Counterion effects

KW - Initio molecular-dynamics

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KW - Practical tool

KW - Complexes

KW - Energy

KW - Pseudopotentials

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