Actinide 5f Occupations: The Case of PuO2

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 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 M5‐edge high energy resolution X‐ray absorption and emission spectroscopic data. The total donation to the metal in PuO2 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 (VB‐RIXS) experiments demonstrate that Pu 5f electron density is present in the valence band; thus, there is a clear experimental signature of covalent bonding in PuO2. Pu M5‐edge and M3‐edge high energy resolution X‐ray absorption near edge structure (HR‐XANES) for Pu3+ and Pu4+ in aqueous solution are compared to PuO2 showing that Pu in PuO2 has n(f) closer to Pu4+(aq).