Hybrid functional for correlated electrons in the projector augmented-wave formalism: Study of multiple minima for actinide oxides

F. Jollet, G. Jomard, B. Amadon, J. P. Crocombette, and D. Torumba

Phys. Rev. B 80, 235109 – Published 3 December 2009

Abstract

Exact (Hartree-Fock) exchange for correlated electrons is implemented to describe correlated orbitals in the projector augmented-waves (PAW) framework, as suggested recently in another context [P. Novák et al., Phys. Status Solidi B 243, 563 (2006)]. Hartree-Fock exchange energy is applied to strongly correlated electrons only inside the PAW atomic spheres. This allows the use of PBE0 hybrid exchange-correlation functional for correlated electrons. This method is tested on NiO and results agree well with already published results and generalized gradient approximation,

GGA + U

calculations. It is then applied to plutonium oxides and

{UO}_{2}

for which the results are comparable with the ones of

GGA + U

calculations but without adjustable parameter. As evidenced in the uranium oxide case, the occurrence of multiple energy minima may lead to very different results depending on the initial electronic configurations and on the symmetries taken into account in the calculation.