Bulk and surface electronic structure of MnPSe3 revealed by photoemission and x-ray absorption spectroscopy

Bulk and surface electronic states of ${\mathrm{MnPSe}}_{3}$ have been investigated by means of x-ray photoemission spectroscopy (XPS), x-ray absorption spectroscopy (XAS), and theoretical calculations. In Mn $2p$ XPS, the main peak is accompanied by a charge-transfer satellite which is commonly observed in various Mn chalcogenides. The intensity of the charge-transfer satellite is considerably reduced by oxidization of the surface. The multiplet structure of Mn $2p$ XAS indicates the high spin ${\mathrm{Mn}}^{2+}$ configuration. The cluster model analyses of the XPS and XAS spectra indicate that the Se $4p$-to-Mn $3d$ charge-transfer energy $\mathrm{\ensuremath{\Delta}}$ is negative providing the strong $p\ensuremath{-}d$ hybridization. The magnetic interaction between the third nearest neighboring Mn spins is enhanced by the smallness of $\mathrm{\ensuremath{\Delta}}$ and the unique molecular orbitals of the ${\mathrm{P}}_{2}{\mathrm{Se}}_{6}$ cluster.