Effect of the chemical state of uranium atom on the energy of spin-orbital splitting of its inner orbitals
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Yuri F. Batrakov
Summary
Chemical shifts (ChSh) of nine emission lines of the uranium L-series in uranium oxides UO2+x (x=0-1) with respect to UO2 were studied by using a precise crystal-diffraction X-ray spectrometer. ChSh of Lα1,α2 uranium and thorium lines in solid solutions yUO2·(1-y )ThO2 (y=0:1) were measured with respect to UO2 and ThO2, respectively. The changes in energy of spin-orbital splitting (SOS) — Δδnl± of inner nl-orbitals of the uranium atom were calculated from the data of ChSh of spin-doublet lines. For UO2+x oxides, a linear decrease in Δδnl± values with increasing degree of uranium oxidation was found. Sign inversion of Δδnl± for uranium levels was found on passing to solid solutions. No change in the SOS energy of inner thorium levels was detected. The values of Δδnl± were found to correlate with the experimental values of the effective magnetic moment of uranium in oxides.
On the basis of the comparison of experimental Δδnl± values with Dirac–Hartree–Fock atomic calculations, it was concluded that the observed variations in Δδnl± values are due to the redistribution of electron and spin density between the 5f7/2- and 5f5/2-levels of the fine structure of the uranium atom without changes in atomic charge state. On the basis of the hypothesis of intraatomic relativistic U5f7/2↔U5f5/2 transition, a model of paramagnetic moment formation on the uranium atom in uranium dioxide was proposed.
© 2004 Oldenbourg Wissenschaftsverlag GmbH
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Articles in the same Issue
- Measurement of cross sections of threshold detectors with spectrum average technique
- Ionic radii of heavy actinide(III) cations
- Effect of the chemical state of uranium atom on the energy of spin-orbital splitting of its inner orbitals
- Heterogeneous catalytic redox reactions of neptunium ions in the aqueous system HNO3-HCOOH
- Field study of the migration of 90Sr, 237Np, 238Pu and 241Am in unsaturated Chinese loess under artificial rainfall condition
- Extraction of tetravalent neptunium isoxazolonates as their TOPO adducts
- Extraction of Eu(III) and Tm(III) with picrolonic acid in methylisobutylketone
- Adsorption of 60Co2+ on hydrous manganese oxide powder from aqueous solution
- Simultaneous multi-element determination in some cosmetic samples of different origins using neutron activation analysis
- Radiolysis of an aqueous [11C]iomazenil solution
