Analysis of state-dependent fluorescence effects and electronic structure in multivalent manganese oxides

Moderate systematic understanding has been established in the literature how different x-ray absorption techniques, i.e., total electron yield, partial fluorescence yield, and inverse partial fluorescence yield, compare and contrast for the ${L}_{2,3}$ edges of transition metal oxides. In this paper, we attempt to analyze and understand trends between different techniques and furthermore shed light on self-absorption effects and state-dependent fluorescence probabilities in fluorescence yield mode. Our experiments demonstrate strong interdependence of the manganese direct fluorescence yield and correlation effects, while the secondary $3s\ensuremath{\rightarrow}2p$ decay as well as inverse partial fluorescence yield are unaffected. We present x-ray absorption, nonresonant x-ray emission, and resonant inelastic x-ray scattering spectra for manganese oxides at the Mn ${L}_{2,3}$ edges and investigate their spectral shape with multiplet ligand field calculations. The collected spectra are sensitive to valence state, local environment, and hybridization. Least-squares optimization of our parametrized ligand field model allows us to analyze the electronic structure of the studied compounds.