Mn3sexchange splitting in mixed-valence manganites

We present Mn $3s$ x-ray photoelectron spectra of manganese oxides with the Mn formal valency from $2+$ to $4+.$ We found that the ${\mathrm{Sr}}^{2+}$ doping or cation deficiency in manganites do not change the Mn $3s$ splitting in manganites with the Mn formal valency from $3.0+$ to $3.3+.$ We suggest that doping holes are localized in O $2p$ states.