Electron correlation and relativistic effects on the electronic properties of a plutonium and americium mixed oxide (PuAmO4): from single-particle approximation to dynamical mean-field theory

Abstract

First-principles calculations were performed on a plutonium and americium mixed oxide (PuAmO₄), aiming at revealing the effects of electron correlation, Pu/Am 5f-conduction electrons’ hybridization, and relativity on its electronic properties. The many-body calculation suggests that the spin–orbit-coupling (SOC)-splitting of j = 5/2 and j = 7/2 manifolds are both in the weakly and moderately correlated states, respectively, implying that the jj coupling scheme is more appropriate for Pu/Am 5f electrons. The density of states, 5f occupation numbers, and Green's functions all suggest that both Pu and Am 5f electrons exhibit the coexistence of the localized and delocalized states. The admixture of 5fⁿ atomic configurations, Pu/Am 5f-conduction electrons’ hybridization, and dual characteristics of 5f electrons yield average occupation numbers of 5f electrons n_5f = 4.78 and 5.86 for Pu and Am ions, respectively. Within the DFT+DMFT calculation, the weighted-summation-derived occupation numbers in terms of 5f⁴/5f⁵/5f⁶ and 5f⁵/5f⁶ configurations for Pu and Am 5f electrons, respectively, are in reasonable agreement with those of other DFT-based calculations.