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Temperature dependence of the X-ray absorption near-edge structure (XANES)spectra at the Pr $L_{3}$- and Tb $L_{3}$-edges was measured for the(Pr$_{1-y}$Tb$_{y})_{0.7}$Ca$_{0.3}$CoO$_{3}$ system, in which ametal-insulator (MI) and spin-state (SS) transition took place simultaneouslyat a critical temperature $T_{\rm MI}$. A small increase in the valence of theterbium ion was found below $T_{\rm MI}$, besides the enhancement of thepraseodymium valence; the trivalent states, which are stable at roomtemperature, change to a 3+/4+ ionic mixture at low temperatures. In particularfor the $y$=0.2 sample, the average valence determined at 8 K amounts to 3.03+and 3.25+ for the Tb and Pr ion, respectively. In analogous(Pr$_{1-y}$RE$_{y})_{0.7}$Ca$_{0.3}$CoO$_{3}$ samples (RE=Sm and Eu), in whichthe MI-SS transition also took place, no valence shift of the RE ion wasdetected in the XANES spectra at the RE ion $L_{3}$-edge. The role of thesubstituted RE ion for the Pr-site on the MI-SS transition is discussed.

Simultaneous valence shift of Pr and Tb ions at the spin-state transition in ((Pr$_{1-y}$Tb$_{y})_{0.7}$Ca$_{0.3}$CoO$_{3}$