The long-wave 5d X-ray spectra of thorium and uranium in compounds with oxygen and fluorine

Lyakhovskaya, I. I.; Ipatov, V. M.; Zimkina, T. M.

doi:10.1007/bf00745286

Cited by 3 publications

(3 citation statements)

References 3 publications

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“…The XPS data on the OVMO and IVMO structures in actinide compounds are qualitatively in line with the results of non-relativistic X a -DV calculation of the electronic structure of the [UO 2 F 5 ] 37 cluster (D 5h group of symmetry) 264 and relativistic X a -DV calculation for the UF 6 , NpF 6 , PuF 6 , 265 UF 6 266 ± 268 and UO 2 (NO 3 ) 2 . 2 H 2 O 204, 269 molecules as well as with the data of X-ray emission, 100,182,185,186,188,234,246,247,259 Auger, 235,236 X-ray absorption, 189,191,270 conversion electron spectroscopy, 218 ± 221 etc.…”

Section: The Spectra Of the An6p And O2s Lns Electronsmentioning

confidence: 63%

The structure of X-ray photoelectron spectra of light actinide compounds

Teterin¹,

Teterin²

2004

Russ. Chem. Rev.

121

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Section: The Spectra Of the An6p And O2s Lns Electronsmentioning

confidence: 63%

The structure of X-ray photoelectron spectra of light actinide compounds

Teterin¹,

Teterin²

2004

Russ. Chem. Rev.

121

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“…1). Lyakhovskaya et al [12] assumed previously that the longwave group of lines is due to the triplet of electronic transitions involving the core (inner) shells of the uranium ions, U5d 5/2, 3/2 4 U6p 3/2, 1/2 ( Fig. 1, Table 1).…”

Section: Conversion Electron Spectroscopy (Ces)mentioning

confidence: 96%

X-Ray Spectral Methods in Investigation of the UO2 Electronic Structure

Teterin

2005

Radiochemistry

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Fine structure of the X-ray photoelectron spectrum of UO 2 at electron binding energies from 0 tõ 40 eV is primarily due to electrons of outer (0 315 eV) and inner (153 40 eV) valence molecular orbitals formed from unoccupied U5f,6d,7s and O2p and occupied low-energy U6p and O2s shells of the neighboring uranium and oxygen atoms, respectively. This is consistent with the results of the relativistic calculation of the electronic structure of the UO 8 12! cluster with O h symmetry, simulating the nearest surrounding of uranium in UO 2 , and is confirmed by the data of X-ray spectroscopy (conversion electron, nonresonance and resonance X-ray O 4, 5 (U) emission, O 4, 5 (U) XANES, photoelectron resonance, and Auger spectroscopy of oxygen). The fine structure of the X-ray photoelectron spectra, associated with electrons from outer valence and inner valence molecular orbitals, allows estimation of the degree of participation of U6p,5f electrons in chemical bonding, as well as the structure of the nearest surrounding of the uranium atom and the bond length in its oxides. The total contribution from electrons of inner valence molecular orbitals to the absolute value of the chemical bonding energy can be compared with the corresponding contribution of the electrons from outer valence molecular orbitals to bonding of the atoms. Inner valence molecular orbitals can be formed in compounds of any elements, and this is an important new fact in chemistry and physics of condensed state.It was traditionally believed that chemical bonds in compounds are formed mostly from electrons of unoccupied low-energy (from 0 to~15 eV) shells of the neighboring atoms. This was favored to a certain extent by a wide use of sources of excitation in the visible and UV regions in spectroscopy of atoms and molecules. X-ray emission spectroscopic studies of various substances were also oriented mostly at these electron energy regions. Although participation of electrons from relatively deep-lying occupied atomic shells (from~15 to~50 eV) in formation of inner valence molecular orbitals (IVMOs) is justified from the quantum-mechanical viewpoint, it was believed that their influence on the interatomic bonds in compounds is negligible compared to the most weakly bound electrons of the outer valence molecular orbitals (OVMOs) (energies from 0 to~15 eV). However, we found recently [133] that, under certain conditions, inner valence molecular orbitals can be formed in compounds of any elements [133]. This is a new, extremely important, scientific fact in chemistry and physics of condensed state, which can hardly be overestimated.In this study, we consider new data on the nature of chemical bonding with UO 2 as an example. These data were obtained using modern X-ray spectral methods such as X-ray photoelectron, conversion electron, nonresonance and resonance X-ray O 4, 5 (U) emission, O 4, 5 (U) XANES, photoelectron resonance, and Auger spectroscopy of oxygen, taking into account the results of the relativistic calculation of the electronic structure of th...

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“…Lyakhovskaya et al [17] analyzed the structure of the O 4, 5 (U) emission spectrum of uranium in oxides, recorded under moderate resolution, assuming that the low-energy structure was due to the triplet of electronic transitions involving the core shells of the uranium ions, U5d 5/2, 3/2 4 U6p 3/2, 1/2 . However, Fig.…”

Section: Resultsmentioning

confidence: 99%

An X-ray Spectral Study of the Electronic Structure of Uranyl Fluoride UO2F2

et al. 2005

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The fine structure of the X-ray photoelectron spectrum of low-energy electrons and O 4,5 (U) X-ray emission spectrum of uranyl fluoride UO 2 F 2 (at binding energies from 0 to 40 eV) was identified on the basis of the electronic structure calculations for the [(UO 2 )F 6 ] 4! cluster with D 6h point symmetry, simulating the nearest surrounding of uranium in UO 2 F 2 , by the relativistic X = discrete variation method. It was shown that the U5f electrons can directly participate in chemical bonding, and U6p electrons, in formation of not only inner valence but also outer valence molecular orbitals. The sequence of the inner valence molecular orbitals in the binding energy region from 12 to 40 eV was established, which is essential for development of a procedure for determining the uranium3ligand bond length in the axial direction and in the equatorial plane of the uranyl compounds, based on the characteristics of their X-ray photoelectron spectra.

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The long-wave 5d X-ray spectra of thorium and uranium in compounds with oxygen and fluorine

Cited by 3 publications

References 3 publications

The structure of X-ray photoelectron spectra of light actinide compounds

The structure of X-ray photoelectron spectra of light actinide compounds

X-Ray Spectral Methods in Investigation of the UO2 Electronic Structure

An X-ray Spectral Study of the Electronic Structure of Uranyl Fluoride UO2F2

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