Crystal structure, valence state of cations and elemental composition of manganite Pr$_{1-x}$Bi$_x$MnO$_{3+\sigma}$

According to X-ray photoelectron spectroscopy, the ratio of the fractions of trivalent and tetravalent manganese, Mn$^{3+}$/Mn$^{4+}$, in ceramic manganite Pr$_{1-x}$Bi$_x$MnO$_{3+\sigma}$ was determined. The profiles of the X-ray photoelectron Pr4$d$- and Mn2$p$-spectra were calculated in the isolated ion approximation considering multiplet splitting in the final state of photoionization, and good agreement with the experiment was achieved.