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  A Complete High-to-Low spin state Transition of Trivalent Cobalt Ion in Octahedral Symmetry in SrCo0.5Ru0.5O3-δ

Chen, J.-M., Chin, Y.-Y., Valldor, M., Hu, Z., Lee, J.-M., Haw, S.-C., et al. (2014). A Complete High-to-Low spin state Transition of Trivalent Cobalt Ion in Octahedral Symmetry in SrCo0.5Ru0.5O3-δ. Journal of the American Chemical Society, 136(4), 1514-1519. doi:10.1021/ja4114006.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0019-0B56-A Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0019-0B59-4
Genre: Journal Article

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 Creators:
Chen, Jin-Ming1, Author
Chin, Yi-Ying2, Author              
Valldor, Martin3, Author              
Hu, Zhiwei4, Author              
Lee, Jenn-Min1, Author
Haw, Shu-Chih1, Author
Hiraoka, Nozomu1, Author
Ishii, Hirofumi1, Author
Pao, Chih-Wen1, Author
Tsuei, Ku-Ding1, Author
Lee, Jyh-Fu1, Author
Lin, Hong-Ji1, Author
Jang, Ling-Yun1, Author
Tanaka, Arata1, Author
Chen, Chien-Te1, Author
Tjeng, Liu Hao5, Author              
Affiliations:
1external, ou_persistent22              
2Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863404              
3Martin Valldor, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863454              
4Zhiwei Hu, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863461              
5Liu Hao Tjeng, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863452              

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 Abstract: The complex metal oxide SrCo0.5Ru0.5O3-δ possesses a slightly distorted perovskite crystal structure. Its insulating nature infers a well-defined charge distribution, and the six-fold coordinated transition metals have the oxidation states +5 for ruthenium and +3 for cobalt as observed by X-ray spectroscopy. We have discovered that Co3+ ion is purely high-spin at room temperature, which is unique for a Co3+ in an octahedral oxygen surrounding. We attribute this to the crystal field interaction being weaker than the Hund’s-rule exchange due to a relatively large mean Co–O distances of 1.98(2) Å, as obtained by EXAFS and X-ray diffraction experiments. A gradual high-to-low spin state transition is completed by applying high hydrostatic pressure of up to 40 GPa. Across this spin state transition, the Co Kβ emission spectra can be fully explained by a weighted sum of the high-spin and low-spin spectra. Thereby is the much debated intermediate spin state of Co3+ absent in this material. These results allow us to draw an energy diagram depicting relative stabilities of the high-, intermediate-, and low-spin states as functions of the metal–oxygen bond length for a Co3+ ion in an octahedral coordination.

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 Dates: 2014-01-29
 Publication Status: Published in print
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 Rev. Method: -
 Identifiers: DOI: 10.1021/ja4114006
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: American Chemical Society
Pages: - Volume / Issue: 136 (4) Sequence Number: - Start / End Page: 1514 - 1519 Identifier: ISSN: 0002-7863
CoNE: /journals/resource/954925376870