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X-ray absorption spectroscopy measurements in Pr0.5Ca0.5CoO3 were performedat the Pr M4,5, Pr L3, and Ca L2,3 absorption edges as a function oftemperature below 300 K. Ca spectra show no changes down to 10 K while anoticeable thermally dependent evolution takes place at the Pr edges across themetal-insulator transition. Spectral changes are analyzed by different methods,including multiple scattering simulations, which provide quantitative detailson an electron loss at Pr 4f orbitals. We conclude that in the insulating phasea fraction [15(+5)%] of Pr3+ undergoes a further oxidation to adopt ahybridized configuration composed of an admixture of atomic-like 4f1 states(Pr4+) and f- symmetry states on the O 2p valence band (Pr3+L states)indicative of a strong 4f- 2p interaction.

Valence change of praseodymium in Pr0.5Ca0.5CoO3 investigated by x-ray absorption spectroscopy