Electronic structure and chemical bond nature in Cs2PuO2Cl4
X-ray photoelectron spectral analysis of dicaesiumtetrachlorodioxoplutonate (Cs2PuO2Cl4) single crystal was done in the binding energy range 0-~35 eV on the basis of binding energies and structure of the core electronic shells (~35 eV-1250 eV), as well as the relativistic discrete variation calculat...
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Published in | Nuclear technology & radiation protection Vol. 30; no. 2; pp. 99 - 112 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
VINCA Institute of Nuclear Sciences
01.01.2015
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Subjects | |
Online Access | Get full text |
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Summary: | X-ray photoelectron spectral analysis of dicaesiumtetrachlorodioxoplutonate
(Cs2PuO2Cl4) single crystal was done in the binding energy range 0-~35 eV on
the basis of binding energies and structure of the core electronic shells
(~35 eV-1250 eV), as well as the relativistic discrete variation calculation
results for the PuO2Cl4 (D4h). This cluster reflects Pu close environment in
Cs2PuO2Cl4 containing the plutonyl group PuO2. The many-body effects due to
the presence of cesium and chlorine were shown to contribute to the outer
valence (0-~15 eV binding energy) spectral structure much less than to the
inner valence (~15 eV- ~35 eV binding energy) one. The filled Pu 5f
electronic states were theoretically calculated and experimentally con-
firmed to present in the valence band of Cs2PuO2Cl4. It corroborates the
suggestion on the direct participation of the Pu 5f electrons in the chemical
bond. The Pu 6p atomic orbitals were shown to participate in formation of
both the inner and the outer valence molecular orbitals (bands), while the
filled Pu 6p and O 2s, Cl 3s electronic shells were found to take the largest
part in formation of the inner valence molecular orbitals. The composition of
molecular orbitals and the sequence order in the binding energy range 0-~35
eV in Cs2PuO2Cl4 were established. The quantitative scheme of molecular
orbitals for Cs2PuO2Cl4 in the binding energy range 0-~15 eV was built on the
basis of the experimental and theoretical data. It is fundamental for both
understanding the chemical bond nature in Cs2PuO2Cl4 and the interpretation
of other X-ray spectra of Cs2PuO2Cl4. The contributions to the chemical
binding for the PuO2Cl4 cluster were evaluated to be: the contribution of the
outer valence molecular orbitals -66 %, the contribution of the inner valence
molecular orbitals -34 %.
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1451-3994 1452-8185 |
DOI: | 10.2298/NTRP1502099T |