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Relativistic Multiconfigurational Ab Initio Calculation of Uranyl 3d4f Resonant Inelastic X-ray Scattering

Polly, Robert; Schacherl, Bianca; Rothe, Jörg; Vitova, Tonya

Abstract (englisch):
We applied relativistic multiconfigurational all-electron ab initio calculations including the spin−orbit interaction to calculate the 3d4f resonant inelastic X-ray scattering (RIXS) map (3d3/2 →5f5/2 U M 4 absorption edge and 4f5/2 →3d3/2 U M βemission) of uranyl (UO22+). The calculated data are in excellent agreement with experimental results and allow a detailed understanding of the observed features and an unambiguous assignment of all involved intermediate and final states. The energies corresponding to the maxima of the resonant emission and the non-resonant (normal) emission were determined with high accuracy, and the corresponding X-ray absorption near edge structure spectra extracted at these two positions were simulated and agree well with the measured data. With the high quality of our theoretical data, we show that the cause of the splitting of the three main peaks in emission is due to the fine structure splitting of the 4f orbitals induced through the trans di-oxo bonds in uranyl and that we are able to obtain direct information about the energy differences between the 5f and 4f orbitals: Δ5f δ/φ−4f δ/φ, Δ5f π*−4f π, and Δ5f σ*−4f σfrom the 3d4f RIXS map. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000140313
Veröffentlicht am 25.11.2021
DOI: 10.1021/acs.inorgchem.1c02364
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nukleare Entsorgung (INE)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2021
Sprache Englisch
Identifikator ISSN: 0020-1669, 1520-510X
KITopen-ID: 1000140313
HGF-Programm 32.11.03 (POF IV, LK 01) Fundamental Scientific Aspects
Weitere HGF-Programme 54.11.11 (POF IV, LK 01) Accelerator Operation, Research and Development
Erschienen in Inorganic chemistry
Verlag American Chemical Society (ACS)
Vorab online veröffentlicht am 24.11.2021
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