Density functional calculations on actinide compounds: Survey of recent progress and application to [UO2X4]2? (X=F, Cl, OH) and AnF6 (An=U, Np, Pu)

Schreckenbach, Georg; Hay, P. Jeffrey; Martin, Richard L.

doi:10.1002/(sici)1096-987x(19990115)20:1<70::aid-jcc9>3.0.co;2-f

Cited by 234 publications

(217 citation statements)

References 202 publications

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“…The electronic structure of the Cm 3+ ion, [Rn]5f 7 , features no unoccupied 5f orbitals; each is half-filled and would experience the lone-pair repulsion observed in Ce 3+ . Because of both the repulsion between oxygen lone pairs and the occupied 5f orbitals of Cm 3+ and the greater geometric extent of the unoccupied 6d, 7s, and 7p orbitals, 65 coordinating solvent molecules do not donate electrons to the 5f orbital. Regardless of whether the coordinating solvent molecule is water or methanol, the donated electrons are distributed approximately 57% in 6d, 27% in 7p, and 16% in 7s, with a negligible amount donated to the 5f orbital.…”

Section: ■ Discussionmentioning

confidence: 99%

Structural and Thermodynamic Properties of the Cm^III Ion Solvated by Water and Methanol

et al. 2016

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The geometric and electronic structures of the 9-coordinate Cm(3+) ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller-Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion-solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion-solvent dissociation energy and the ion-solvent distance are shown to be dependent on the solvent-shell composition. This has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.

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Section: ■ Discussionmentioning

confidence: 99%

Structural and Thermodynamic Properties of the Cm^III Ion Solvated by Water and Methanol

et al. 2016

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“…It should be noted that a systematic investigation of density functional method validation for computing structures of rare earth aqua ions has been reported in [27,31]. The best-known hybrid Becke's three-parameter with LeeYang-Parr correlation term B3LYP functional is generally considered more appropriate for transition metal chemistry, as this method is known to reproduce accurate geometries and thermochemistries for transition metals complexes [32][33]. However, our studies [27,31] on the structural characteristics of octahydrated Y 3+ and nonahydrated La 3+ aqua ions suggest that the standard B3LYP technique may not be the best possible for such systems.…”

Section: Methodsmentioning

confidence: 99%

Ab initio and DFT study of Lu3+ hydration

Buz’ko¹,

Sukhno²,

Buz’ko³

2009

Journal of Molecular Structure: THEOCHEM

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“…From the experimental point of view the limited availability of most actinide elements and their severe radioactivity are the main obstacles. For quantum chemical first-principle studies of systems containing actinide elements, the main challenge arises from the significant contributions of relativity as well as electron correlation [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Quasirelativistic energy-consistent 5f-in-core pseudopotentials for trivalent actinide elements

2006

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Quasirelativistic energy-consistent 5f-in-core pseudopotentials modelling trivalent actinides, corresponding to a near-integral 5f n occupation (n = 0-14 for Ac-Lr), have been generated. Energy-optimized (6s5p4d), (7s6p5d), and (8s7p6d) primitive valence basis sets contracted to polarized double to quadruple zeta quality as well as 2f1g correlation functions have been derived. Corresponding smaller basis sets (4s4p3d), (5s5p4d), and (6s6p5d) suitable for calculations on actinide(III) ions in crystalline solids form subsets of these basis sets designed for calculations on neutral molecules. Results of Hartree-Fock test calculations for actinide(III) monohydrates and actinide trifluorides show a satisfactory agreement with corresponding calculations using 5f-in-valence pseudopotentials. Even in the beginning of the actinide series, where the 5f shell is relatively diffuse, only quite acceptable small deviations occur as long as the 5f-shell does not participate significantly in covalent bonding.

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Density functional calculations on actinide compounds: Survey of recent progress and application to [UO2X4]2? (X=F, Cl, OH) and AnF6 (An=U, Np, Pu)

Cited by 234 publications

References 202 publications

Structural and Thermodynamic Properties of the Cm^III Ion Solvated by Water and Methanol

Structural and Thermodynamic Properties of the Cm^III Ion Solvated by Water and Methanol

Ab initio and DFT study of Lu3+ hydration

Quasirelativistic energy-consistent 5f-in-core pseudopotentials for trivalent actinide elements

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Density functional calculations on actinide compounds: Survey of recent progress and application to [UO2X4]2? (X=F, Cl, OH) and AnF6 (An=U, Np, Pu)

Cited by 234 publications

References 202 publications

Structural and Thermodynamic Properties of the CmIII Ion Solvated by Water and Methanol

Structural and Thermodynamic Properties of the CmIII Ion Solvated by Water and Methanol

Ab initio and DFT study of Lu3+ hydration

Quasirelativistic energy-consistent 5f-in-core pseudopotentials for trivalent actinide elements

Contact Info

Product

Resources

About

Structural and Thermodynamic Properties of the Cm^III Ion Solvated by Water and Methanol

Structural and Thermodynamic Properties of the Cm^III Ion Solvated by Water and Methanol