Abstract
Oxidation state is a key chemical quantity that allows the understanding and prediction of the majority of chemical reactions; however, the main deficiency using the formal oxidation state comes from the materials containing multivalent metals. Among them, the most complicated element plutonium (Pu) is an outstanding instance. Here, we calculate the orbital occupation numbers under the frameworks of first-principles density functional theory (DFT) + U methods to quantitatively determine the Pu-oxidation state of the recently reported complex molecular solids: [K(crypt)]Pu[C5H3(SiMe3)2]3, Pu3(DPA)5(H2O)2, and Pu3(DPA)6H. The results show that the oxidation state of Pu is an extremely low Pu2+ in the former and a mixed Pu3+/Pu4+ in the latter two compounds, which is consistent with the experimental identifications. The steric effects and the environmentally sensitive localization → delocalization transition of Pu 5f electrons can rationally elucidate the formation of the unusual oxidation states. Such atomi...
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