We combine Mn L2,3-edge X-ray absorption, high resolution Mn 2p - 3d - 2p resonant X-ray emission, and configuration - interaction full-multiplet (CIFM) calculation to analyze the electronic structure of Mn-based Prussian blue analogue. We clarified the Mn 3d energy diagram for the Mn2+ low-spin state separately from that of the Mn2+ high-spin state by tuning the excitation energy for the X-ray emission measurement. The obtained X-ray emission spectra are generally reproduced by the CIFM calculation for the Mn2+ low spin state having a stronger ligand-to-metal charge-transfer effect between Mn t2g and CN π orbitals than the Mn2+ high spin state. The d - d-excitation peak nearest to the elastic scattering was ascribed to the Mn2+ LS state by the CIFM calculation, indicating that the Mn2+ LS state with a hole on the t2g orbital locates near the Fermi level. (Chemical Equation Presented).
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