Valence XPS structure and chemical bond in Cs2UO2Cl4
Quantitative analysis was done of the valence electrons X-ray photoelectron spectra structure in the binding energy (BE) range of 0 eV to ~35 eV for crystalline dicaesium tetrachloro-dioxouranium (VI) (Cs2UO2Cl4). This compound contains the uranyl group UO2. The BE and structure of the core...
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| Language: | English |
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VINCA Institute of Nuclear Sciences
2016-01-01
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| Series: | Nuclear Technology and Radiation Protection |
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| Online Access: | http://www.doiserbia.nb.rs/img/doi/1451-3994/2016/1451-39941601037T.pdf |
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| author | Teterin Yury A. Maslakov Konstantin I. Ryzhkov Mikhail V. Teterin Anton Yu. Ivanov Kirill E. Kalmykov Stepan N. Petrov Vladimir G. Suglobov Dmitry N. |
| author_facet | Teterin Yury A. Maslakov Konstantin I. Ryzhkov Mikhail V. Teterin Anton Yu. Ivanov Kirill E. Kalmykov Stepan N. Petrov Vladimir G. Suglobov Dmitry N. |
| author_sort | Teterin Yury A. |
| collection | DOAJ |
| description | Quantitative analysis was done of the valence electrons X-ray photoelectron
spectra structure in the binding energy (BE) range of 0 eV to ~35 eV for
crystalline dicaesium tetrachloro-dioxouranium (VI) (Cs2UO2Cl4). This
compound contains the uranyl group UO2. The BE and structure of the core
electronic shells (~35 eV-1250 eV), as well as the relativistic discrete
variation calculation results for the UO2Cl4(D4h) cluster reflecting U close
environment in Cs2UO2Cl4 were taken into account. The experimental data show
that many-body effects due to the presence of cesium and chlorine contribute
to the outer valence (0-~15 eV BE) spectral structure much less than to the
inner valence (~15 eV-~35 eV BE) one. The filled U5f electronic states were
theoretically calculated and experimentally confirmed to be present in the
valence band of Cs2UO2Cl4. It corroborates the suggestion on the direct
participation of the U5f electrons in the chemical bond. Electrons of the U6p
atomic orbitals participate in formation of both the inner (IVMO) and the
outer (OVMO) valence molecular orbitals (bands). The filled U6p and the O2s,
Cl3s electronic shells were found to make the largest contributions to the
IVMO formation. The molecular orbitals composition and the sequence order in
the binding energy range 0 eV-~35 eV in the UO2Cl4 cluster were established.
The experimental and theoretical data allowed a quantitative molecular
orbitals scheme for the UO2Cl4 cluster in the BE range 0-~35 eV, which is
fundamental for both understanding the chemical bond nature in Cs2UO2Cl4 and
the interpretation of other X-ray spectra of Cs2UO2Cl4. The contributions to
the chemical binding for the UO2Cl4 cluster were evaluated to be: the OVMO
contribution - 76%, and the IVMO contribution - 24 %. |
| first_indexed | 2024-12-21T08:22:28Z |
| format | Article |
| id | doaj.art-4c1c83a622f74a9282b158b07e3d0b4a |
| institution | Directory Open Access Journal |
| issn | 1451-3994 1452-8185 |
| language | English |
| last_indexed | 2024-12-21T08:22:28Z |
| publishDate | 2016-01-01 |
| publisher | VINCA Institute of Nuclear Sciences |
| record_format | Article |
| series | Nuclear Technology and Radiation Protection |
| spelling | doaj.art-4c1c83a622f74a9282b158b07e3d0b4a2022-12-21T19:10:24ZengVINCA Institute of Nuclear SciencesNuclear Technology and Radiation Protection1451-39941452-81852016-01-01311375010.2298/NTRP1601037T1451-39941601037TValence XPS structure and chemical bond in Cs2UO2Cl4Teterin Yury A.0Maslakov Konstantin I.1Ryzhkov Mikhail V.2Teterin Anton Yu.3Ivanov Kirill E.4Kalmykov Stepan N.5Petrov Vladimir G.6Suglobov Dmitry N.7NRC “Kurchatov Institute”, Moscow, Russia + Lomonosov Moscow State University, Chemistry Department, Moscow, RussiaLomonosov Moscow State University, Chemistry Department, Moscow, RussiaInstitute of Solid State Chemistry, Ural Department of RAS, Ekaterinburg, RussiaNRC “Kurchatov Institute”, Moscow, RussiaLomonosov Moscow State University, Chemistry Department, Moscow, RussiaLomonosov Moscow State University, Chemistry Department, Moscow, RussiaLomonosov Moscow State University, Chemistry Department, Moscow, RussiaV.G. Khlopin Radium Institute, St. Petersburg, RussiaQuantitative analysis was done of the valence electrons X-ray photoelectron spectra structure in the binding energy (BE) range of 0 eV to ~35 eV for crystalline dicaesium tetrachloro-dioxouranium (VI) (Cs2UO2Cl4). This compound contains the uranyl group UO2. The BE and structure of the core electronic shells (~35 eV-1250 eV), as well as the relativistic discrete variation calculation results for the UO2Cl4(D4h) cluster reflecting U close environment in Cs2UO2Cl4 were taken into account. The experimental data show that many-body effects due to the presence of cesium and chlorine contribute to the outer valence (0-~15 eV BE) spectral structure much less than to the inner valence (~15 eV-~35 eV BE) one. The filled U5f electronic states were theoretically calculated and experimentally confirmed to be present in the valence band of Cs2UO2Cl4. It corroborates the suggestion on the direct participation of the U5f electrons in the chemical bond. Electrons of the U6p atomic orbitals participate in formation of both the inner (IVMO) and the outer (OVMO) valence molecular orbitals (bands). The filled U6p and the O2s, Cl3s electronic shells were found to make the largest contributions to the IVMO formation. The molecular orbitals composition and the sequence order in the binding energy range 0 eV-~35 eV in the UO2Cl4 cluster were established. The experimental and theoretical data allowed a quantitative molecular orbitals scheme for the UO2Cl4 cluster in the BE range 0-~35 eV, which is fundamental for both understanding the chemical bond nature in Cs2UO2Cl4 and the interpretation of other X-ray spectra of Cs2UO2Cl4. The contributions to the chemical binding for the UO2Cl4 cluster were evaluated to be: the OVMO contribution - 76%, and the IVMO contribution - 24 %.http://www.doiserbia.nb.rs/img/doi/1451-3994/2016/1451-39941601037T.pdfactinideuraniumelectronic structureXPSrelativistic calculation |
| spellingShingle | Teterin Yury A. Maslakov Konstantin I. Ryzhkov Mikhail V. Teterin Anton Yu. Ivanov Kirill E. Kalmykov Stepan N. Petrov Vladimir G. Suglobov Dmitry N. Valence XPS structure and chemical bond in Cs2UO2Cl4 Nuclear Technology and Radiation Protection actinide uranium electronic structure XPS relativistic calculation |
| title | Valence XPS structure and chemical bond in Cs2UO2Cl4 |
| title_full | Valence XPS structure and chemical bond in Cs2UO2Cl4 |
| title_fullStr | Valence XPS structure and chemical bond in Cs2UO2Cl4 |
| title_full_unstemmed | Valence XPS structure and chemical bond in Cs2UO2Cl4 |
| title_short | Valence XPS structure and chemical bond in Cs2UO2Cl4 |
| title_sort | valence xps structure and chemical bond in cs2uo2cl4 |
| topic | actinide uranium electronic structure XPS relativistic calculation |
| url | http://www.doiserbia.nb.rs/img/doi/1451-3994/2016/1451-39941601037T.pdf |
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