Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study
Abstract The pressure-response of the Co-O bond lengths and the spin state of Co ions in a hybrid 3d-5d solid-state oxide Sr2Co0.5Ir0.5O4 with a layered K2NiF4-type structure was studied by using hard X-ray absorption and emission spectroscopies. The Co-K and the Ir-L 3 X-ray absorption spectra demo...
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Nature Portfolio
2017
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oai:doaj.org-article:e5a02c989ec646f2971b9a6100eba4f82021-12-02T12:32:33ZRelation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study10.1038/s41598-017-03950-z2045-2322https://doaj.org/article/e5a02c989ec646f2971b9a6100eba4f82017-06-01T00:00:00Zhttps://doi.org/10.1038/s41598-017-03950-zhttps://doaj.org/toc/2045-2322Abstract The pressure-response of the Co-O bond lengths and the spin state of Co ions in a hybrid 3d-5d solid-state oxide Sr2Co0.5Ir0.5O4 with a layered K2NiF4-type structure was studied by using hard X-ray absorption and emission spectroscopies. The Co-K and the Ir-L 3 X-ray absorption spectra demonstrate that the Ir5+ and the Co3+ valence states at ambient conditions are not affected by pressure. The Co Kβ emission spectra, on the other hand, revealed a gradual spin state transition of Co3+ ions from a high-spin (S = 2) state at ambient pressure to a complete low-spin state (S = 0) at 40 GPa without crossing the intermediate spin state (S = 1). This can be well understood from our calculated phase diagram in which we consider the energies of the low spin, intermediate spin and high spin states of Co3+ ions as a function of the anisotropic distortion of the octahedral local coordination in the layered oxide. We infer that a short in-plane Co-O bond length (<1.90 Å) as well as a very large ratio of Co-Oapex/Co-Oin-plane is needed to stabilize the IS Co3+, a situation which is rarely met in reality.Yi-Ying ChinHong-Ji LinZhiwei HuChang-Yang KuoDaria MikhailovaJenn-Min LeeShu-Chih HawShin-An ChenWalter SchnelleHirofumi IshiiNozomu HiraokaYen-Fa LiaoKu-Ding TsueiArata TanakaLiu Hao TjengChien-Te ChenJin-Ming ChenNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 7, Iss 1, Pp 1-9 (2017) |
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DOAJ |
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| topic |
Medicine R Science Q |
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Medicine R Science Q Yi-Ying Chin Hong-Ji Lin Zhiwei Hu Chang-Yang Kuo Daria Mikhailova Jenn-Min Lee Shu-Chih Haw Shin-An Chen Walter Schnelle Hirofumi Ishii Nozomu Hiraoka Yen-Fa Liao Ku-Ding Tsuei Arata Tanaka Liu Hao Tjeng Chien-Te Chen Jin-Ming Chen Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study |
| description |
Abstract The pressure-response of the Co-O bond lengths and the spin state of Co ions in a hybrid 3d-5d solid-state oxide Sr2Co0.5Ir0.5O4 with a layered K2NiF4-type structure was studied by using hard X-ray absorption and emission spectroscopies. The Co-K and the Ir-L 3 X-ray absorption spectra demonstrate that the Ir5+ and the Co3+ valence states at ambient conditions are not affected by pressure. The Co Kβ emission spectra, on the other hand, revealed a gradual spin state transition of Co3+ ions from a high-spin (S = 2) state at ambient pressure to a complete low-spin state (S = 0) at 40 GPa without crossing the intermediate spin state (S = 1). This can be well understood from our calculated phase diagram in which we consider the energies of the low spin, intermediate spin and high spin states of Co3+ ions as a function of the anisotropic distortion of the octahedral local coordination in the layered oxide. We infer that a short in-plane Co-O bond length (<1.90 Å) as well as a very large ratio of Co-Oapex/Co-Oin-plane is needed to stabilize the IS Co3+, a situation which is rarely met in reality. |
| format |
article |
| author |
Yi-Ying Chin Hong-Ji Lin Zhiwei Hu Chang-Yang Kuo Daria Mikhailova Jenn-Min Lee Shu-Chih Haw Shin-An Chen Walter Schnelle Hirofumi Ishii Nozomu Hiraoka Yen-Fa Liao Ku-Ding Tsuei Arata Tanaka Liu Hao Tjeng Chien-Te Chen Jin-Ming Chen |
| author_facet |
Yi-Ying Chin Hong-Ji Lin Zhiwei Hu Chang-Yang Kuo Daria Mikhailova Jenn-Min Lee Shu-Chih Haw Shin-An Chen Walter Schnelle Hirofumi Ishii Nozomu Hiraoka Yen-Fa Liao Ku-Ding Tsuei Arata Tanaka Liu Hao Tjeng Chien-Te Chen Jin-Ming Chen |
| author_sort |
Yi-Ying Chin |
| title |
Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study |
| title_short |
Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study |
| title_full |
Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study |
| title_fullStr |
Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study |
| title_full_unstemmed |
Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study |
| title_sort |
relation between the co-o bond lengths and the spin state of co in layered cobaltates: a high-pressure study |
| publisher |
Nature Portfolio |
| publishDate |
2017 |
| url |
https://doaj.org/article/e5a02c989ec646f2971b9a6100eba4f8 |
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