Evolution of electronic structure with dimensionality in divalent nickelates

Abstract

We investigate the evolution of electronic structure with dimensionality (d) of Ni-O-Ni connectivity in divalent nickelates, NiO (3-d), La₂NiO₄, Pr₂NiO₄ (2-d), Y₂BaNiO₅ (1-d) and Lu₂BaNiO₅ (0-d), by analyzing the valence band and the Ni 2p core-level photoemission spectra in conjunction with detailed many-body calculations including full multiplet interactions. Experimental results exhibit a reduction in the intensity of correlation-induced satellite features with decreasing dimensionality. The calculations based on the cluster model, but evaluating both Ni 3d and O 2p related photoemission processes on the same footing, provide a consistent description of both valence-band and core-level spectra in terms of various interaction strengths. While the correlation-induced satellite features in NiO is dominated by poorly screened d⁸ states as described in the existing literature, we find that the satellite features in the nickelates with lower dimensional Ni-O-Ni connectivity are in fact dominated by the over-screened d¹⁰L⁻² states. It is found that the changing electronic structure with the dimensionality is primarily driven by two factors: (i) a suppression of the nonlocal contribution to screening; and (ii) a systematic decrease of the charge-transfer energy Δ driven by changes in the Madelung potential.