XANES and X-ray photoemission of the La0.67(Ca,Pb)0.33(Mn1−xFex)O3 compounds

High energy resolution fluorescence detected XANES and the core-level X-ray electron photoemission spectra of lead and iron substituted manganese perovskites La0.67(Ca,Pb)0.33(Mn1−xFex)O3 with x=0, 0.01, 0.03, 0.06, 0.10 and 0.15 were measured and analyzed. The evolution of the average valence of manganese ions was derived from the energy shift of the Mn K-edge as a function of iron content, which changes by ∼0.25 eV from x=0.0 to x=0.15. This agrees well with the expected average valence evolution from Mn3.33+ to Mn3.38+. The relative ratio of Mn3+/Mn4+ was calculated as a function of x by means of multiplet analysis of the Mn 2p3/2 photoemission lines. They are in fairly good agreement with the expected values.