Electronic structure and ligand field states of tetrachlorodioxoneptunate(2-) and trinitratodioxoneptunate(1-): a relativistic MS-X.alpha. study

Makhyoun, M. A.

doi:10.1021/ic00268a034

Cited by 11 publications

(11 citation statements)

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“…Such a weakening of the actinyl bond was already observed in analogous uranyl complexes and attributed to a decrease in the electronic population of bonding NpO yl σ and π orbitals along with an increase of the electrostatic repulsion between the O yl oxygen atoms and the equatorial ligands 81. 82 Quasi‐relativistic MS‐Xα calculations for [NpO 2 (NO 3 ) 3 ] − gave NpO yl =1.732 and NpO eq =2.469 Å, which differ from our results 83. However, the Xα functional tends to over‐bind strongly and is not expected to balance the axial (O yl ) and equatorial Np–ligand interactions correctly.…”

Section: Resultscontrasting

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: Resultscontrasting

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 of the NpO 2 Cl 4 2− ion has been investigated theoretically and experimentally by several authors [6][7][8][9][33][34][35][36][37]. In particular, analyses of optical absorption spectra of oriented single crystals of Cs 2 U(Np)O 2 Cl 4 at liquid helium temperature reveal 5f u → 5f u and LMCT vibronic transitions [9,33].…”

Section: Resultsmentioning

confidence: 99%

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

Wilkerson

Arrington

Berg

et al. 2007

Journal of Alloys and Compounds

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“…Its electronic spectrum has been reported and studied. [77][78][79][80][81][82][83][84][85] Theoretical calculations 61,[86][87][88][89][90] have added to the understanding of the features of the spectrum. Several of the questions regarding neptunyl are related to those of uranyl.…”

Section: Introductionmentioning

confidence: 99%

“…Some calculations have been reported with equatorial ligands around the uranyl 50,56,[59][60][61][62][63][66][67][68]72,73 or neptunyl 61,62,68,89 ion. The ligands varied from fluorides and chlorides to nitrates, sulfates, carbonates, hydroxides, water molecules, and even just point charges.…”

Section: Introductionmentioning

confidence: 99%

“…Interestingly, Schreckenbach et al 66 found local minima for UO 2 (OH) 4 2-with a bent uranyl unit only 18-19 kcal/mol higher in energy than the global minimum. Makhyoun 89 calculated f f f transitions for NpO 2 Cl 4 2-and NpO 2 (NO 3 ) 3 -using the X R and Slater transition-state procedures. 91 We model the Cs 2 UO 2 Cl 4 crystal in trying to answer questions concerning the influence of the crystal environment on the spectroscopy 76 of actinyl ions.…”

Section: Introductionmentioning

confidence: 99%

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Actinyl Ions in Cs₂UO₂Cl₄

Matsika

Pitzer

2000

J. Phys. Chem. A

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The electronic energy levels of the uranyl ion (UO 2 2+ ) and the neptunyl ion (NpO 2 2+ ) in the crystalline environment of Cs 2 UO 2 Cl 4 are studied theoretically and compared with the spectroscopic work of Denning and co-workers. A layered-cluster computational method is used. The valence electrons of the actinyl ion and the nearest-neighbor chloride ions are treated explicitly, the closest cesium ions are replaced by all-electron core potentials, and all ions further away are replaced by point charges. The cluster is approximately spherical overall and contains 1873 ions. For the electrons treated explicitly, we use relativistic quantum chemical theory, including relativistic effective core potentials, corresponding spin-orbit operators, and spin-orbit, graphical unitary group configuration interaction. The effects of the crystalline environment on bond distances, vibrational frequencies, excitation energies, energy splittings, and wave function character are examined. Shifts are generally more accurate than absolute values, and the electron correlation treatment is generally the limiting factor in the accuracy.

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Electronic structure and ligand field states of tetrachlorodioxoneptunate(2-) and trinitratodioxoneptunate(1-): a relativistic MS-X.alpha. study

Cited by 11 publications

References 0 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

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

Actinyl Ions in Cs₂UO₂Cl₄

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Electronic structure and ligand field states of tetrachlorodioxoneptunate(2-) and trinitratodioxoneptunate(1-): a relativistic MS-X.alpha. study

Cited by 11 publications

References 0 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

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

Actinyl Ions in Cs2UO2Cl4

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Actinyl Ions in Cs₂UO₂Cl₄