Electronic structure and ESCA shake-up of the UF6 molecule

Larsson, Sven; Tse, John S.; Esquivel, Jonathan; Kai, Aldwyn Tang

doi:10.1016/0301-0104(84)85295-7

Cited by 13 publications

(6 citation statements)

References 33 publications

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“…The difficulties are due to complicated electron correlation effects, to significant scalar relativistic (SR) and spin–orbit coupling (SOC) effects, to the large number of valence and semicore electrons in actinide atoms, and to the complexity of electronic configurations owing to f-electrons. A number of theoretical investigations has been carried out on the ground-state properties of UF 6 , including geometries, electronic structures and spectroscopic properties, using ab initio wave function theory (WFT) and density functional theory (DFT). − …”

Section: Introductionmentioning

confidence: 99%

Excited States and Absorption Spectra of UF₆: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Fan

Schwarz

et al. 2011

J. Chem. Theory Comput.

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Uranium hexafluoride (UF6) is an important compound in nuclear chemistry. The theoretical investigation of its excited states is difficult due to the large number of uranium valence orbitals and ligand lone pairs. We report here a detailed relativistic quantum chemical investigation of its excited states up to about 10 eV using restricted active space second-order perturbation theory (RASPT2). Scalar and spin-orbit (SO) relativistic effects are treated by a relativistic small-core pseudopotential. The RASPT2/SO results remain moderately accurate when the electrons in the active space are restricted to single and double excitations. All eight major spectral peaks corresponding to ligand-to-metal charge transfer have been reproduced within an accuracy of about 0.2 eV and are tentatively assigned. We find that BLYP-based hybrid density functional with 35% Hartree-Fock exchange well reproduce the excitation energies of UF6.

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Section: Introductionmentioning

confidence: 99%

Excited States and Absorption Spectra of UF₆: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Fan

Schwarz

et al. 2011

J. Chem. Theory Comput.

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“…Uranium hexafluoride, UF 6 , is perhaps the most extensively studied actinide molecule, both experimentally − and theoretically. − On the other hand, derivatives of UF 6 where the fluorine ligands are successively replaced by some other ligand L, UF 6 - n L n ( n = 1−6), have received much less attention so far.…”

Section: Introductionmentioning

confidence: 99%

Mixed Uranium Chloride Fluorides UF₆_-_nCl_nand Methoxyuranium Fluorides UF₆_-_n(OCH₃)_n: A Theoretical Study of Equilibrium Geometries, Vibrational Frequencies, and the Role of the f Orbitals

Schreckenbach

2000

Inorg. Chem.

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The title compounds, the uranium (VI) fluoride chlorides (UF6-nCln, n = 0-6) and methoxyuranium (VI) fluorides [UF6-n(OCH3)n, n = 0-5], have been studied using relativistic density functional theory. Applying the B3LYP hybrid functional and an effective core potential on uranium, equilibrium geometries have been calculated for these molecules. In addition, harmonic vibrational frequencies have been computed for the chloride fluorides. Calculated frequencies have been compared to experiment where possible. All experimentally observed bands have been assigned, based on these calculations. The average deviation between theoretical and experimental frequencies is 15.6 cm-1 for 23 experimental modes. Theory always underestimates the experimental frequencies. This can be explained by the calculated bond lengths that are somewhat too long. The electronic structure of the uranium (VI) chloride fluorides has been investigated using scalar relativistic calculations and the PW91 functional. Periodic trends in the role and bonding contribution of the uranium 5f orbitals are discussed.

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“…(In the following this reaction will be referred as the key reaction.) For this reason, UF 6 has become a prototype molecule for a considerable amount of experimental − and theoretical − work.…”

Section: Introductionmentioning

confidence: 99%

A Relativistic Density Functional Study on the Uranium Hexafluoride and Plutonium Hexafluoride Monomer and Dimer Species

et al. 1998

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A study on the UF 6 monomer and dimer was carried out within the density functional method. The U-F distance in the UF 6 monomer was optimized at different levels of theory, pointwise, assuming octahedral geometry, (1) by using an all-electron basis for both U and F in a nonrelativistic calculation; (2) by using a relativistic effective core potential (RECP) on U and nonrelativistic effective core potential (ECP) on the fluorines; and (3) by using RECP on the U atom and an all-electron basis on the F atoms. Atomization energies of 23.11, 33.92, and 35.66 eV were obtained at the three levels, respectively. Relativistic effects lead to about a 50% increase in the atomization energy. For the UF 6 dimer, the potential energy curve, as a function of the intermolecular U-U distance, was computed at level 2, and the rotational barrier between the two monomers was determined. Similar calculations were performed on the corresponding PuF 6 species. Comparisons are made with experiment and other theoretical studies, where available.

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Electronic structure and ESCA shake-up of the UF6 molecule

Cited by 13 publications

References 33 publications

Excited States and Absorption Spectra of UF₆: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Excited States and Absorption Spectra of UF₆: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Mixed Uranium Chloride Fluorides UF₆_-_nCl_nand Methoxyuranium Fluorides UF₆_-_n(OCH₃)_n: A Theoretical Study of Equilibrium Geometries, Vibrational Frequencies, and the Role of the f Orbitals

A Relativistic Density Functional Study on the Uranium Hexafluoride and Plutonium Hexafluoride Monomer and Dimer Species

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Electronic structure and ESCA shake-up of the UF6 molecule

Cited by 13 publications

References 33 publications

Excited States and Absorption Spectra of UF6: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Excited States and Absorption Spectra of UF6: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Mixed Uranium Chloride Fluorides UF6-nClnand Methoxyuranium Fluorides UF6-n(OCH3)n: A Theoretical Study of Equilibrium Geometries, Vibrational Frequencies, and the Role of the f Orbitals

A Relativistic Density Functional Study on the Uranium Hexafluoride and Plutonium Hexafluoride Monomer and Dimer Species

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Product

Resources

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Excited States and Absorption Spectra of UF₆: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Excited States and Absorption Spectra of UF₆: A RASPT2 Theoretical Study with Spin–Orbit Coupling

Mixed Uranium Chloride Fluorides UF₆_-_nCl_nand Methoxyuranium Fluorides UF₆_-_n(OCH₃)_n: A Theoretical Study of Equilibrium Geometries, Vibrational Frequencies, and the Role of the f Orbitals