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Actinide 5f Occupations: The Case of PuO 2

Bajaj, Ashima [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:000000021179063X)·Ramanantoanina, Harry [Karlsruhe Inst. of Technology (KIT) (Germany)]·Schacherl, Bianca [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000345420108)·Schenk, Sven [Karlsruhe Inst. of Technology (KIT) (Germany)]·Pruessmann, Tim [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000279039199)·Tasi, Agost [Karlsruhe Inst. of Technology (KIT) (Germany)]·Fellhauer, David [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000274400790)·Humiston, Alaina [Illinois Inst. of Technology Chicago, IL (United States)]·Terry, Jeff [Illinois Inst. of Technology Chicago, IL (United States)] (ORCID:0000000178813667)·Wang, Xiaoyu [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:0000000175496010)·Zurek, Eva [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:000000030738867X)·Vitova, Tonya [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000231177701)·Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)]·Autschbach, Jochen [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:000000019392877X)
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Abstract

In actinide chemistry, the formal number of open-shell 5f electrons, n open , is a well-defined quantity with an integer value. The effective 5f occupation, n f , additionally takes donation and back-donation into account, generally has a non-integer value, and has varying numerical definitions. The present study explores the important distinction between n f and n open in actinide chemistry with the example of PuO2, by using electronic structure methods with a relativistic Hamiltonian in combination with experimental Pu M 5 -edge high-energy-resolution X-ray absorption and emission spectroscopic data. The total donation to the metal in PuO 2 is between 3.1 and 2.4 electrons, depending on the type of calculation, most of which is to the Pu 6d and 5f shells. The donation into 5f is sensitive to the approximations in the electronic structure model but likely amounts to 1.6/0.8 electrons when the diffuse regions of the 5f shell are included/excluded. Valence band resonant inelastic X-ray scattering experiments demonstrate that Pu 5f electron density is present in the valence band; thus, there is a clear experimental signature of covalent bonding in PuO 2 . Pu M 5 -edge and M 3 -edge high-energy-resolution X-ray absorption near-edge structures for Pu 3+ and Pu 4+ in an aqueous solution are compared to PuO 2 , showing that Pu in PuO 2 has an nf closer to Pu 4+ (aq).

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYChemical calculationsElectronic structureEnergyFourier transformsOrganic polymers

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Bajaj, Ashima [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:000000021179063X), Ramanantoanina, Harry [Karlsruhe Inst. of Technology (KIT) (Germany)], Schacherl, Bianca [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000345420108), Schenk, Sven [Karlsruhe Inst. of Technology (KIT) (Germany)], Pruessmann, Tim [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000279039199), Tasi, Agost [Karlsruhe Inst. of Technology (KIT) (Germany)], Fellhauer, David [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000274400790), Humiston, Alaina [Illinois Inst. of Technology Chicago, IL (United States)], Terry, Jeff [Illinois Inst. of Technology Chicago, IL (United States)] (ORCID:0000000178813667), Wang, Xiaoyu [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:0000000175496010), Zurek, Eva [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:000000030738867X), Vitova, Tonya [Karlsruhe Inst. of Technology (KIT) (Germany)] (ORCID:0000000231177701), Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)], Autschbach, Jochen [State Univ. of New York (SUNY), Buffalo, NY (United States)] (ORCID:000000019392877X). 2025-06-10. Actinide 5f Occupations: The Case of PuO 2. https://doi.org/10.1021/acs.inorgchem.5c01709

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