Nuclear Technology & Radiation Protection Journal


NT & RP Journal	ELECTRONIC STRUCTURE AND CHEMICAL BOND NATURE IN Cs₂PuO₂Cl₄
......: info......: history......: editorial......: archive......: for authors......: subscription
Vol. XXX, No. 2, Pp. 83-163 June 2015 UDC 621.039+614.876:504.06 ISSN 1451-3994 Back to Contents	Pages: 99-112 Authors: Yury A. Teterin, Konstantin I. Maslakov, Mikhail V. Ryzhkov, Anton Yu. Teterin, Kirill E. Ivanov, Stepan N. Kalmykov, Vladimir G. Petrov, and Dmitry N. Suglobov Abstract 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 PuO₂Cl₄^2- (D_4h). This cluster reflects Pu close environment in Cs₂PuO₂Cl₄ containing the plutonyl group PuO₂²⁺. 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 confirmed 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 PuO₂Cl₄^2- cluster were evaluated to be: the contribution of the outer valence molecular orbitals –66 %, the contribution of the inner valence molecular orbitals –34 %. Key words: X-ray photoelectron spectroscopy, valence molecular orbitals, plutonyl group FULL PAPER IN PDF FORMAT (2.06 MB)
Vinča Institute of Nuclear Sciences :: Designed by milas :: July 2007 Operated by acapanic :: Last updated on August 2015

Pages: 99-112

Authors: Yury A. Teterin, Konstantin I. Maslakov, Mikhail V. Ryzhkov, Anton Yu. Teterin, Kirill E. Ivanov, Stepan N. Kalmykov, Vladimir G. Petrov, and Dmitry N. Suglobov

Abstract
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 PuO₂Cl₄^2- (D_4h). This cluster reflects Pu close environment in Cs₂PuO₂Cl₄ containing the plutonyl group PuO₂²⁺. 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 confirmed 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 PuO₂Cl₄^2- cluster were evaluated to be: the contribution of the outer valence molecular orbitals –66 %, the contribution of the inner valence molecular orbitals –34 %.

Key words: X-ray photoelectron spectroscopy, valence molecular orbitals, plutonyl group

FULL PAPER IN PDF FORMAT (2.06 MB)