Valence-state transition inSrMn1−xMoxO3(0≤x≤0.5)investigated by soft x-ray absorption spectroscopy

Abstract

The electronic structures of perovskite ${\text{SrMn}}_{1\ensuremath{-}x}{\text{Mo}}_{x}{\text{O}}_{3}$ $(0\ensuremath{\le}x\ensuremath{\le}0.5)$ have been investigated by employing soft x-ray absorption spectroscopy (XAS). $\text{Mn}\text{ }2p$ XAS shows the systematic change in the valence states of Mn ions in ${\text{SrMn}}_{1\ensuremath{-}x}{\text{Mo}}_{x}{\text{O}}_{3}$ due to the substitution of hexavalent ${\text{Mo}}^{6+}(4{d}^{0})$ ions. With increasing $x$, the valence states and the spin configurations of Mn ions change from high-spin (HS) ${\text{Mn}}^{4+}$ for $x=0$, to HS ${\text{Mn}}^{3+}({t}_{2g}^{3}\ensuremath{\uparrow}{e}_{g}^{1}\ensuremath{\uparrow})$ for $x=0.3$, and HS ${\text{Mn}}^{2+}({t}_{2g}^{3}\ensuremath{\uparrow}{e}_{g}^{2}\ensuremath{\uparrow})$ for $x=0.5$. The measured $\text{Mn}\text{ }2p$ XAS spectra are described well with the configuration interaction (CI) cluster model, including the Jahn-Teller distortion effect for ${\text{Mn}}^{3+}$ ions. The combination of the findings of $\text{Mn}\text{ }2p$ XAS and the CI calculations provides the complete picture of the electronic structures of ${\text{SrMn}}_{1\ensuremath{-}x}{\text{Mo}}_{x}{\text{O}}_{3}$ for $0\ensuremath{\le}x\ensuremath{\le}0.5$.