Distinguishing between High- and Low-Spin States for Divalent Mn in Mn-Based Prussian Blue Analogue by High-Resolution Soft X-ray Emission Spectroscopy.
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 Mn(2+) low-spin state separately from that of the Mn(2+) 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 Mn(2+) low spin state having a stronger ligand-to-metal charge-transfer effect between Mn t2g and CN π orbitals than the Mn(2+) high spin state. The d-d-excitation peak nearest to the elastic scattering was ascribed to the Mn(2+) LS state by the CIFM calculation, indicating that the Mn(2+) LS state with a hole on the t2g orbital locates near the Fermi level.
†Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan.
Daisuke
D
Asakura
†Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan.
Yusuke
Y
Nanba
†Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan.
Masashi
M
Okubo
†Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan.
Yoshifumi
Y
Mizuno
‡Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan.|§Synchrotron Radiation Research Organization, The University of Tokyo, Bunkyo-ku, Tokyo 113-8586, Japan.
Hideharu
H
Niwa
§Synchrotron Radiation Research Organization, The University of Tokyo, Bunkyo-ku, Tokyo 113-8586, Japan.
Masaharu
M
Oshima
†Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan.
Haoshen
H
Zhou
∥The Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530, Japan.
Kozo
K
Okada
‡Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan.|§Synchrotron Radiation Research Organization, The University of Tokyo, Bunkyo-ku, Tokyo 113-8586, Japan.
Yoshihisa
Y
Harada
Prussian blue analogue; charge transfer; multiplet calculation; resonant soft X-ray emission spectroscopy; soft X-ray absorption spectroscopy; spin state