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Role of Spin-Orbital Splitting of 5f-Orbitals of Uranium Atom in the Formation of Its Chemical State

Published online by Cambridge University Press:  01 February 2011

Yuri F. Batrakov ,
Andrey G. Krivitsky  and
Elena V. Puchkova
Yuri F. Batrakov
Affiliation:
Department of Radiochemistry, Faculty of Chemistry, St. Petersburg State University, 7/9 Universitetskaja emb., St. Petersburg, 199034, Russia Email: x-ray@ak11168.spb.edu
Andrey G. Krivitsky
Affiliation:
Department of Radiochemistry, Faculty of Chemistry, St. Petersburg State University, 7/9 Universitetskaja emb., St. Petersburg, 199034, Russia Email: x-ray@ak11168.spb.edu
Elena V. Puchkova
Affiliation:
Department of Radiochemistry, Faculty of Chemistry, St. Petersburg State University, 7/9 Universitetskaja emb., St. Petersburg, 199034, Russia Email: x-ray@ak11168.spb.edu
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Abstract

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 and 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.

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 5f 7/2- and 5f 5/2-levels of the fine structure of the uranium atom without changes in atomic charge state.

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Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 802: Symposium DD – Actinides - Basic Science, Applications, and Technology , 2003 , DD5.4
Copyright
Copyright © Materials Research Society 2004

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References

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