X-ray spectra and valence states of cations in nanostructured half-doped $$\hbox {La}_{0.5}\hbox {Ca}_{0.5}\hbox {MnO}_{3}$$ manganite

Soft X-ray absorption (XAS) and emission (XES) spectroscopies were applied to determine valence states of manganese ions in nanostructured powder of half-doped \(\hbox {La}_{0.5}\hbox {Ca}_{0.5}\hbox {MnO}_{3}\) manganite obtained by milling in a ball mill. XAS spectra were measured both in surface-sensitivity total electron-yield and in bulk-sensitivity total fluorescence-yield modes. O K\(_{\upalpha }\) XES and O 1s XAS spectra characterized the occupied and unoccupied partial O 2p densities of states are compared with band-structure calculations made using the TB-LMTO-ASA codes. Experimental Mn 2p, Ca 2p, and La 3\(d\) XAS spectra are compared with results of crystal field atomic multiplet calculations. For the nanostructured system of \(\hbox {La}_{0.5}\hbox {Ca}_{0.5}\hbox {MnO}_{3}\), concentrations of Mn\(^{4+}\) ions are found to be increased with increasing the time of milling.