Charge-Transfer Electronic Structure of NiX${}_2$ (X = S, Se)

Abstract

We investigate the electronic structures of NiS${}_2$ and NiSe${}_2$ using density functional theory combined with dynamical mean-field theory (DFT+DMFT). A realistic electronic structure within DFT+DMFT was determined by optimizing the double-counting correction to reproduce experimental valence-band photoemission spectra. The validity of the present model is further confirmed by its successful description of the Ni 2$p$ core-level photoemission and Ni $L$-edge x-ray absorption spectra of NiS${}_2$. Our results reveal a smaller charge-transfer energy than previously assumed, resulting in substantial ligand-to-Ni charge transfer and a reduced Ni local moment. We clarify how the relative position and interaction between the Ni upper Hubbard band and the antibonding chalcogen-dimer states shape the evolution of the low-energy electronic structure across the NiS${}_{2-x}$Se${}_x$ series.