Local structure and oxidation state of Mn and Ni atoms in LaNi1-xMnxO3+δ perovskites

Abstract

X-ray absorption spectroscopy has been used to study LaNi1-x MnxO3+δ perovskites (x= 0.1, 0.25, 0.5, 0.75, 0.9). We have analysed both, the oxidation state and the local structure around the transition metal atoms. XANES spectra of these samples suggest a mixed valence state for both transition metal atoms. The Mn K-edge is shifted to high energies as the Ni content is increased up to x=0.5. The opposite behavior is found instead, for the Ni K-edge. Samples with x=0.5 and x=0.25 present the Mn K -edge at the same energy but the absorption features are different for both samples. The local structure has also been studied by means of the EXAFS technique. The first coordination shell nicely reflects the structural change observed in this series from rhombohedral perovskites (x>0.5) to orthorhombic perovskites (x<0.5). The changes in the local structure for Ni and Mn atoms agree with the variation of the oxidation state observed in the XANES spectra.