Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 123, Issue 19, Pages 12096-12103Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.9b01527
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Funding
- Science Challenge Project of China [TZ2016004]
- National Natural Science Foundation of China [21771167, 21701006]
- Foundation of President of China Academy of Engineering Physics [YZJJSQ2017072]
- Foundation of Science and Technology on Surface Physics and Chemistry Laboratory [WDZC201802]
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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), Pu-3(DPA)(5)(H2O)(2), and Pu-3(DPA)(6)H. The results show that the oxidation state of Pu is an extremely low Pu-2 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 atomic-resolution quantitative determination of the unusual Pu oxidation states in the complex molecular solids offers an alternative for the further exploration of peculiar Pu solid-state materials.
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