1. First-principles explorations of the universal picture of oxide layer structure over metallic plutonium.
- Author
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Ao, Bingyun and Qiu, Ruizhi
- Subjects
- *
PLUTONIUM oxides , *PLUTONIUM , *CROSS-entropy method , *OXIDES , *OXIDATION states , *CERIUM oxides - Abstract
• The general trends of stability of stoichiometric and non-stoichiometric Pu oxides are firstly reported. • A rigorous quantum definition of oxidation state is used to determine the atomic ratio of Pu3+/Pu4+ in Pu oxides. • The proposed ladder-like Pu oxide layer structure might be more reasonable than the sandwich-like structure. The oxide layer structure over Pu is the central issue of Pu corrosion science; however, the widely discussed sandwich-like structure (Pu//Pu 2 O 3 //PuO 2) might be just a phenomenological description. Here we perform first-principles calculations with the method verification on Ce oxides, the ideal analogues of Pu oxides, to establish a universal picture of Pu oxide layer structure. The results show that homogeneous Pu n O 2 n -2 between PuO 2 and Pu 2 O 3 are energetically more favorable than PuO 2- x with ordered arrays of oxygen vacancies. Thus, a ladder-like oxide layer structure is proposed to improve a simple sandwich-like model of the Pu oxide layers. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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