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

Research output: Contribution to journalArticle

13 Citations (Scopus)


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).

Original languageEnglish
Pages (from-to)4008-4013
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number22
Publication statusPublished - Nov 20 2014



  • Absorption spectroscopy
  • Charge transfer
  • Multiplet calculation
  • Prussian blue analogue
  • Resonant soft X-ray emission spectroscopy
  • Soft X-ray
  • Spin state

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this