First-principles local density approximation+U and generalized gradient approximation+U study of plutonium oxides

Abstract

The electronic structure and properties of PuO2 and Pu2O3 have been studied from first principles by the all-electron projector-augmented-wave method. The local density approximation+U and the generalized gradient approximation+U formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Pu 5f electrons. We discuss how the properties of PuO2 and Pu2O3 are affected by the choice of U as well as the choice of exchange-correlation potential. Also, oxidation reaction of Pu2O3, leading to formation of PuO2, and its dependence on U and exchange-correlation potential have been studied. Our results show that by choosing an appropriate U, it is promising to correctly and consistently describe structural, electronic, and thermodynamic properties of PuO2 and Pu2O3, which enable the modeling of redox process involving Pu-based materials possible.