First-principles LDA+U and GGA+U study of plutonium oxides

Bo Sun; Ping Zhang; Xian-Geng Zhao

paper

First-principles LDA+U and GGA+U study of plutonium oxides

arXiv:0712.3623

Abstract

The electronic structure and properties of PuO $_{2}$ and Pu $_{2}$ O $_{3}$ have been studied from first principles by the all-electron projector-augmented-wave (PAW) method. The local density approximation (LDA)+ $U$ and the generalized gradient approximation (GGA)+ $U$ formalism have been used to account for the strong on-site Coulomb repulsion among the localized Pu $5 f$ electrons. We discuss how the properties of PuO $_{2}$ and Pu $_{2}$ O $_{3}$ are affected by the choice of $U$ as well as the choice of exchange-correlation potential. Also, oxidation reaction of Pu $_{2}$ O $_{3}$ , leading to formation of PuO $_{2}$ , 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 PuO $_{2}$ and Pu $_{2}$ O $_{3}$ , which enables it possible the modeling of redox process involving Pu-based materials.

To appear in J. Chem. Phys