Distinguishing between High- and Low-Spin States for Divalent Mn in Mn-Based Prussian Blue Analogue by High-Resolution Soft X-ray Emission Spectroscopy

Daisuke Asakura; Yusuke Nanba; Masashi Okubo; Yoshifumi Mizuno; Hideharu Niwa; Masaharu Oshima; Haoshen Zhou; Kozo Okada; Yoshihisa Harada

doi:10.1021/jz501738m

Distinguishing between High- and Low-Spin States for Divalent Mn in Mn-Based Prussian Blue Analogue by High-Resolution Soft X-ray Emission Spectroscopy

J Phys Chem Lett. 2014 Nov 20;5(22):4008-13. doi: 10.1021/jz501738m. Epub 2014 Nov 5.

Authors

Daisuke Asakura¹, Yusuke Nanba¹, Masashi Okubo¹, Yoshifumi Mizuno¹, Hideharu Niwa^{2

3}, Masaharu Oshima³, Haoshen Zhou¹, Kozo Okada⁴, Yoshihisa Harada^{2

3}

Affiliations

¹ †Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan.
² ‡Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan.
³ §Synchrotron Radiation Research Organization, The University of Tokyo, Bunkyo-ku, Tokyo 113-8586, Japan.
⁴ ∥The Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530, Japan.

PMID: 26276486
DOI: 10.1021/jz501738m

Abstract

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.

Keywords: Prussian blue analogue; charge transfer; multiplet calculation; resonant soft X-ray emission spectroscopy; soft X-ray absorption spectroscopy; spin state.