Controlled-valence properties ofLa1−xSrxFeO3andLa1−xSrxMnO3studied by soft-x-ray absorption spectroscopy

Abstract

The controlled-valence properties of ${\mathrm{La}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Sr}}_{\mathit{x}}$${\mathrm{FeO}}_{3}$ and ${\mathrm{La}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Sr}}_{\mathit{x}}$${\mathrm{MnO}}_{3}$ are studied by means of soft-x-ray absorption spectroscopy. A comparison between the transition-metal 2p spectra and atomic-multiplet calculations is used to determine the 3d count. The O 1s spectrum is used to characterize changes in unoccupied states that contain oxygen p character. The results indicate that the holes induced by substitution for both series are located in states of mixed metal 3d--oxygen 2p character. The ground state of ${\mathrm{LaFeO}}_{3}$ is mainly 3${\mathit{d}}^{5}$ and becomes 3${\mathit{d}}^{5}$L (where L denotes a ligand hole) in the ${\mathrm{La}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Sr}}_{\mathit{x}}$${\mathrm{FeO}}_{3}$ series for low Sr concentration. The main component of the ground state of ${\mathrm{LaMnO}}_{3}$ is 3${\mathit{d}}^{4}$ and becomes a mixture of 3${\mathit{d}}^{3}$ and 3${\mathit{d}}^{4}$L in the ${\mathrm{La}}_{1\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Sr}}_{\mathit{x}}$${\mathrm{MnO}}_{3}$ series. The trends in controlled- valence properties of similar oxides across the transition-metal series can be rationalized within the framework of the Zaanen-Sawatzky-Allen model.