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

详细信息    查看全文

• 作者：Daisuke Asakura ; Yusuke Nanba ; Masashi Okubo ; Yoshifumi Mizuno ; Hideharu Niwa ; Masaharu Oshima ; Haoshen Zhou ; Kozo Okada ; Yoshihisa Harada
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2014
• 出版时间：November 20, 2014
• 年：2014
• 卷：5
• 期：22
• 页码：4008-4013
• 全文大小：314K
• ISSN：1948-7185

文摘

We combine Mn L_2,3-edge X-ray absorption, high resolution Mn 2p鈥?d鈥?p resonant X-ray emission, and configuration鈥搃nteraction 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 t_2g and CN 蟺 orbitals than the Mn²⁺ high spin state. The d鈥揹-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 t_2g orbital locates near the Fermi level.

Keywords:

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