The electronic structure of actinyl ions

Denning, R.G.; Norris, J.O.W.; Brown, Dylan

doi:10.1080/00268978200101261

Cited by 58 publications

(130 citation statements)

References 21 publications

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“…20 The absorption spectrum of NpO 2 2+ was also recorded in the form doped into Cs 2 UO 2 Cl 4 and CsUO 2 (NO 3 ) 3 crystals. [21][22][23][24][25] These latter spectra were similar to the solution ones implying that the transition energies are not much affected by the environment. The ground electronic states could be well determined on the basis of the above experiments: they are the 3 .…”

Section: +supporting

confidence: 60%

“…Selected experimental 20,23,24 and theoretical [29][30][31]33,34 results of NpO 2 2+ are compared in Table V. In the experimental spectra, five bands (two in solution 20 and five in the Cs 2 UO 2 Cl 4 crystal 23 ) have been identified as 5f-5f electronic transitions from the ground state to low-lying excited states.…”

Section: +mentioning

confidence: 99%

“…[16][17][18][19][20][23][24][25][30][31][32][33][34][35] Due to the environment influencing considerably the spectral intensities in solutions and solids, our Einstein coefficients computed for the isolated molecules may not be suited for comparison. In contrast, the transition energies suffer less from the environment.…”

Section: +mentioning

confidence: 99%

“…12,19,[23][24][25][26][29][30][31][32][33][34][35]38,39 We computed the excited electronic states up to ca. 35 000 cm −1 using the SO-CASPT2 method.…”

Section: +mentioning

confidence: 99%

“…The ground electronic states could be well determined on the basis of the above experiments: they are the 3 . 23,24,26 The electronic spectra of the solutions were first assigned using semi-empirical ligand-field theory (NpO 2 +27 and NpO 2 2+ 28 ) and were revised later by quantum chemical calculations. 19,25,[29][30][31][32][33][34][35] Matsika et al 19,25,29 used configuration interaction methods in conjunction with relativistic effective core potentials that incorporate also spin-orbit coupling 36 (SO-MRCI).…”

Section: +mentioning

confidence: 99%

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Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

Kovács

Infante

2015

The Journal of Chemical Physics

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The electronic of neutral NpO and NpO2 as well as of their mono- (NpO+, NpO2+) and dications (NpO2+, NpO22+) were studied using multiconfigurational relativistic quantum chemical calculations at the complete active space self-consistent field/CASPT2 level of taking into account The active space included 16 orbitals: all the 7s, 6d, and 5f orbitals of together with selected orbitals of oxygen. The vertical on the geometries have been computed up to ca. 35 000 cm−1. The gas-phase electronic were evaluated on the basis of the computed Einstein coefficients at 298 K and 3000 K. The computed vertical transition show good agreement with previous condensed-phase results on NpO2+ and NpO22+.

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Section: +supporting

confidence: 60%

Section: +mentioning

confidence: 99%

Section: +mentioning

confidence: 99%

“…12,19,[23][24][25][26][29][30][31][32][33][34][35]38,39 We computed the excited electronic states up to ca. 35 000 cm −1 using the SO-CASPT2 method.…”

Section: +mentioning

confidence: 99%

Section: +mentioning

confidence: 99%

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Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

Kovács

Infante

2015

The Journal of Chemical Physics

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Electronic Structure of the Actinide Elements

Gendron

Autschbach

2018

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The electronic structure of actinide elements and complexes thereof is discussed in the context of first‐principles theory, with emphasis on the interplay of relativistic effects and static correlation, spin–orbit coupling, and the importance of ligand‐field interactions in actinide complexes. Selected actinide complexes are discussed in detail in order to illustrate these effects. It is also shown how the open 5f shells of actinides give rise to interesting magnetic properties.

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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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The electronic structure of actinyl ions

Cited by 58 publications

References 21 publications

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

Electronic Structure of the Actinide Elements

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

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