First-principles modeling of localized d states with the GW@LDA+U approach

Article

关键词: DENSITY-FUNCTIONAL THEORY;    SELF-CONSISTENT GW;    RANDOM-PHASE-APPROXIMATION;    TRANSITION-METAL OXIDES;    BAND-STRUCTURE CALCULATIONS;    ELECTRONIC-STRUCTURE;    CRYSTAL-FIELD;    NIO;    ENERGY;    MNO;   

DOI  :  10.1103/PhysRevB.82.045108

来源: SCIE

【 摘 要 】

First-principles modeling of systems with localized d states is currently a great challenge in condensed-matter physics. Density-functional theory in the standard local-density approximation (LDA) proves to be problematic. This can be partly overcome by including local Hubbard U corrections (LDA+U) but itinerant states are still treated on the LDA level. Many-body perturbation theory in the GW approach offers both a quasiparticle perspective (appropriate for itinerant states) and an exact treatment of exchange (appropriate for localized states), and is therefore promising for these systems. LDA+U has previously been viewed as an approximate GW scheme. We present here a derivation that is simpler and more general, starting from the static Coulomb-hole and screened exchange approximation to the GW self-energy. Following our previous work for f-electron systems [H. Jiang, R. I. Gomez-Abal, P. Rinke, and M. Scheffler, Phys. Rev. Lett. 102, 126403 (2009)] we conduct a systematic investigation of the GW method based on LDA+U (GW@LDA+U), as implemented in our recently developed all-electron GW code FHI-gap (Green's function with augmented plane waves) for a series of prototypical d-electron systems: (1) ScN with empty d states, (2) ZnS with semicore d states, and (3) late transition-metal oxides (MnO, FeO, CoO, and NiO) with partially occupied d states. We show that for ZnS and ScN, the GW band gaps only weakly depend on U but for the other transition-metal oxides the dependence on U is as strong as in LDA+U. These different trends can be understood in terms of changes in the hybridization and screening. Our work demonstrates that GW@LDA+U with physical values of U provides a balanced and accurate description of both localized and itinerant states.

【 授权许可】

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