Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Wilkerson, Marianne P.; Arrington, Caleb A.; Berg, John M.; Scott, Brian L.

doi:10.1016/j.jallcom.2006.12.011

Cited by 25 publications

(51 citation statements)

References 29 publications

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“…These optimized distances agree reasonably well with experimental crystal structure data for [NpO 2 Cl 4 ] 2− obtained in different environments, in which NpO yl ranges from 1.766 to 1.775 Å and NpCl ranges from 2.653 to 2.670 Å 87. 88 For comparison, interatomic distances obtained from X‐ray diffraction were reported as NpO yl =1.731–1.737 Å and NpO eq =2.452–2.469 Å for crystals of M[NpO 2 (NO 3 ) 3 ], with M=NH 4 − , K − , and Rb − 89. 90…”

Section: Resultsmentioning

confidence: 99%

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models

Gendron

Páez‐Hernández

Notter

et al. 2014

Chemistry A European J

152

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The electronic structure and magnetic properties of neptunyl(VI), NpO2(2+), and two neptunyl complexes, [NpO2(NO3)3](-) and [NpO2Cl4](2-), were studied with a combination of theoretical methods: ab initio relativistic wavefunction methods and density functional theory (DFT), as well as crystal-field (CF) models with parameters extracted from the ab initio calculations. Natural orbitals for electron density and spin magnetization from wavefunctions including spin-orbit coupling were employed to analyze the connection between the electronic structure and magnetic properties, and to link the results from CF models to the ab initio data. Free complex ions and systems embedded in a crystal environment were studied. Of prime interest were the electron paramagnetic resonance g-factors and their relation to the complex geometry, ligand coordination, and nature of the nonbonding 5f orbitals. The g-factors were calculated for the ground and excited states. For [NpO2Cl4](2-), a strong influence of the environment of the complex on its magnetic behavior was demonstrated. Kohn-Sham DFT with standard functionals can produce reasonable g-factors as long as the calculation converges to a solution resembling the electronic state of interest. However, this is not always straightforward.

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Section: Resultsmentioning

confidence: 99%

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models

Gendron

Páez‐Hernández

Notter

et al. 2014

Chemistry A European J

152

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“…101 We thereby utilized 102 . 105 We explored two different possibilities for the central unit: (a) one where it was split into NpO 2 2+ and Cl 4 4À , and only NpO 2 2+ was treated using IHFSCC, while the ligands were taken into account with different degrees of sophistication (from simple point charges to densities fully relaxed in freeze-and-thaw cycles); and (b) one where the entire NpO 2 Cl 4 2À is calculated with IHFSCC. Our results are summarized in Table 3, which displays the symmetry classification and excitation energies for the different f-f states following the ordering found in the experimental Table 1 TD-DFT and CC2 n -p excitation energies (ho i i, in eV) for acetone in gas-phase and solution, calculated as oscillator strengthweighted averages over the CP-MD snapshots, together with the corresponding solvatochromic shifts.…”

Section: Results and Discussion A Solvatochromic Shifts Of Acetonmentioning

confidence: 99%

Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory

Gomes

Jacob

Visscher

2008

Phys. Chem. Chem. Phys.

165

247

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We present a simple and efficient embedding scheme for the wave-function based calculation of the energies of local excitations in large systems. By introducing an embedding potential obtained from density-functional theory (DFT) it is possible to describe the effect of an environment on local excitations of an embedded system in wave-function theory (WFT) calculations of the excitation energies. We outline the implementation of such a WFT-in-DFT embedding procedure employing the ADF, Dalton and DIRAC codes, where the embedded subsystem is treated with coupled cluster methods. We then evaluate this procedure in the calculation of the solvatochromic shift of acetone in water and of the f-f spectrum of NpO22+ embedded in a Cs2UO2Cl4 crystal and find that our scheme does effectively incorporate the environment effect in both cases. A particularly interesting finding is that with our embedding scheme we can model the equatorial Cl- ligands in NpO2Cl42- quite accurately, compared to a fully wavefunction-based calculation, and this opens up the possibility of modeling the interaction of different ligands to actinyl species with relatively high accuracy but at a much reduced computational cost.

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“…As such, this ion has pseudo-D 4h symmetry. Details of the molecular structure of Cs 2 NpO 2 Cl 4 are reported elsewhere [16]. Cs 2 NpO 2 Cl 4 is isostructural with Cs 2 UO 2 Cl 4 [17].…”

Section: Structural Characterizationmentioning

confidence: 99%

Excitation spectra of near-infrared photoluminescence from Np(VI) in Cs₂U(Np)O₂Cl₄

Wilkerson¹,

Berg

2009

Radiochimica Acta

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Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Cited by 25 publications

References 29 publications

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models

Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory

Excitation spectra of near-infrared photoluminescence from Np(VI) in Cs₂U(Np)O₂Cl₄

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Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4

Cited by 25 publications

References 29 publications

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal‐Field Models

Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory

Excitation spectra of near-infrared photoluminescence from Np(VI) in Cs2U(Np)O2Cl4

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Excitation spectra of near-infrared photoluminescence from Np(VI) in Cs₂U(Np)O₂Cl₄