First-principles explorations of the universal picture of oxide layer structure over metallic plutonium

• DOI: 10.1016/j.corsci.2019.03.047
• Publication Date: 2019-04-02T11:08:27Z
• Authors: Bingyun Ao; Ruizhi Qiu
• Keywords: 0103 physical sciences; 01 natural sciences

Abstract The oxide layer structure over Pu is the central issue of Pu corrosion science; however, the widely discussed sandwich-like structure (Pu//Pu2O3//PuO2) 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 PunO2n-2 between PuO2 and Pu2O3 are energetically more favorable than PuO2-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.