title: Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO(n)F(8-2n) (n = 0-4).
abstract: While the oxidation state Pu(VIII) is shown to be less stable than Pu(V) in the PuO4 molecule, it is not clear if the more electronegative fluorine can help to stabilize Pu(VIII). Our calculations on PuO(n)F(8-2n) (n = 0-4) molecules notably confirm that PuO2F4 has both (1)D(4h) and (5)C(2v) minima with the oxidation states Pu(VIII) and Pu(V), respectively, with the latter having lower energy. The hybrid-DFT, CCSD(T), and CASSCF methods all give the same result. The results conform to a superoxide ligand when n ≥ 2. PuF8 in a (1)O(h) state can decompose to PuF6 and F2, and PuOF6 in a (1)C(2v) state also can break down to PuF6 and 1/2 O2. The Pu(VIII) anion PuO2F5(-) does have a D(5h) minimum, which also lies above a (5)C(2v) Pu(V) peroxide structure. However, the energy differences between the different minima are not large, indicating that metastable species with oxidation states higher than Pu(V) cannot be completely excluded.
authors: Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University , 100084 Beijing, People's Republic of China.
authors: Wei
authors: W
authors: Huang
authors: Department of Chemistry, University of Helsinki , POB 55, A. I. Virtasen aukio 1, 00014 Helsinki, Finland.
authors: Pekka
authors: P
authors: Pyykkö
authors: Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University , 100084 Beijing, People's Republic of China.
authors: Jun
authors: J
authors: Li