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The wide tunability of strongly correlated transition metal (TM) oxides stems from their complex electronic properties and the coupled degrees of freedom. Among the perovskite oxides family, LaMO3 (M = Ti-Ni) allows an M-dependent systematic study of the electronic structure within the same-structure-family motif. While most of the studies have been focusing on the 3d TMs and oxygen sites, the role of the rare-earth site has been far less explored. In this work, we use resonant inelastic X-ray scattering (RIXS) at the lanthanum N4,5 edges and density functional theory (DFT) to investigate the hybridization mechanisms in LaMO3. We link the spatial-overlap-driven hybridization to energetic-overlap-driven hybridization by comparing the RIXS chemical shifts and the DFT band widths. The scope is extended to highly covalent Ruddlesden-Popper perovskite La2CuO4 by intercalating lanthanum atoms to rock-salt layers. Our work evidences an observable contribution of localized lanthanum 5p and 4f orbitals in the band structure.

In heterogeneous catalysis the surface-adsorbate bond strength is critical for the function of the system. Here we study a series consisting of multilayer, bilayer and monolayer N2O on Ni(111) and employ Auger-photoelectron coincidence spectroscopy (APECS) to study the interaction between the molecule and the substrate directly. We observe intensity in the nitrogen Auger spectra that arise from the interaction between molecule and surface (not observed in free molecules) whereas the oxygen spectra are thickness-independent. Since the two nitrogen atoms of N2O are chemically inequivalent we can assign the intensity present in the bilayer and monolayer cases to orbitals centered on the terminal nitrogen which is closest to the Ni(111) surface. Using ab initio, molecular dynamics and solid-state density functional theory calculations we infer a Blyholder model of the surface bond as consisting of donation from the terminal nitrogen lone-pair valence orbital with back-donation from the metal into the unoccupied orbitals on that nitrogen. This coincidence technique can readily be used to study substrate–adsorbate interactions directly with chemical and orbital specificity — this opens up prospects to study fundamental steps of molecular adsorption and heterogeneous catalysis with unprecedented detail.