Hubbard-U corrected Hamiltonians for non-self-consistent random-phase approximation total-energy calculations: A study of ZnS, TiO2, and NiO

摘要

In non-self-consistent calculations of the total energy within the random-phase approximation (RPA) for electronic correlation, it is necessary to choose a single-particle Hamiltonian whose solutions are used to construct the electronic density and noninteracting response function. Here we investigate the effect of including a Hubbard-U term in this single-particle Hamiltonian, to better describe the on-site correlation of 3d electrons in the transitionmetal compounds ZnS, TiO2, and NiO. We find that the RPAlattice constants are essentially independent of U, despite large changes in the underlying electronic structure. We further demonstrate that the non-self-consistent RPA total energies of these materials have minima at nonzero U. Our RPA calculations find the rutile phase of TiO2 to be more stable than anatase independent of U, a result which is consistent with experiments and qualitatively different from that found from calculations employingU-corrected (semi) local functionals. However we also find that the +U term cannot be used to correct the RPA's poor description of the heat of formation of NiO.