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A method using the ^2H-NMR spectra was shown to be useful to study the solid state physics in diamagnetic and paramagnetic compounds and in crystals having a modulated structure. The spectra and T_1 of NMR in solids were measured for [M(H_2O)_6][AB_6] crystals to investigate the static and dynamic structure of H_2O and [M(H_2O)_6]^\u003c2+\u003e as well as the dynamics of the electron spin in the paramagnetic M^\u003c2+\u003e ion. The physical properties of [M(H_2O)_6][AB_6] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M^\u003c2+\u003e in [M(H_2O)_6][SiF_6] (M^\u003c2+\u003e = Fe^\u003c2+\u003e, Co^\u003c2+\u003e, Ni^\u003c2+\u003e) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin of Cu^\u003c2+\u003e in [Cu(H_2O)_6][PtCl_6] is caused by jumping between the Jahn-Teller configurations. 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固体NMR法による [M(H2O)6][AB6] 結晶における分子及び電子スピンのダイナミクスの研究
http://hdl.handle.net/2297/28457
http://hdl.handle.net/2297/2845762c716ba-52d1-4232-bc1c-359759abf50f
名前 / ファイル | ライセンス | アクション |
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SC-PR-MIZUNO-M-157.pdf (446.9 kB)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2017-10-03 | |||||
タイトル | ||||||
タイトル | 固体NMR法による [M(H2O)6][AB6] 結晶における分子及び電子スピンのダイナミクスの研究 | |||||
タイトル | ||||||
言語 | en | |||||
タイトル | Molecular and electron-spin dynamics in [M(H_2O)_6][AB_6] as studied by solid state NMR | |||||
言語 | ||||||
言語 | jpn | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | journal article | |||||
著者 |
飯島, 隆広
× 飯島, 隆広× 水野, 元博× 須原, 正彦× 遠藤, 一央 |
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書誌情報 |
分析化学 = Japan analyst 巻 52, 号 3, p. 157-163, 発行日 2003-03-05 |
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ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 0525-1931 | |||||
NCID | ||||||
収録物識別子タイプ | NCID | |||||
収録物識別子 | AN00222633 | |||||
DOI | ||||||
関連タイプ | isIdenticalTo | |||||
識別子タイプ | DOI | |||||
関連識別子 | 10.2116/bunsekikagaku.52.157 | |||||
出版者 | ||||||
出版者 | 日本分析化学会 = The Japan Society for Analytical Chemistry | |||||
抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | 固体NMR法は,物質中の分子やイオンの静的・動的局所構造や常磁性イオンの電子スピンのダイナミクスを調べるのに有効な手法である.本研究では,反磁性化合物と常磁性化合物及び変調構造を有する化合物のNMR解析を可能にし,一般式[M(H_2O)_6][AB_6] (M = Mg^<2+>, Mn^<2+>, Fe^<2+>, Co^<2+>, Ni^<2+>; AB_6 = PtCl_6, SiF_6)で表される一連の化合物について,固体NMR法によりH_2O分子や[M(H_2O)_6]^<2+>イオンの静的・動的局所構造及び常磁性M^<2+>イオンの電子スピンのダイナミクスを調べた.分子運動と構造相転移との相関や[M(H_2O)_6]^<2+>イオンの構造と運動性との相関を明らかにした.[M(H_2O)_6]^<2+>イオンのdynamic disorder構造や変調構造も解析された. A method using the ^2H-NMR spectra was shown to be useful to study the solid state physics in diamagnetic and paramagnetic compounds and in crystals having a modulated structure. The spectra and T_1 of NMR in solids were measured for [M(H_2O)_6][AB_6] crystals to investigate the static and dynamic structure of H_2O and [M(H_2O)_6]^<2+> as well as the dynamics of the electron spin in the paramagnetic M^<2+> ion. The physical properties of [M(H_2O)_6][AB_6] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M^<2+> in [M(H_2O)_6][SiF_6] (M^<2+> = Fe^<2+>, Co^<2+>, Ni^<2+>) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin of Cu^<2+> in [Cu(H_2O)_6][PtCl_6] is caused by jumping between the Jahn-Teller configurations. (2) In [Cu(H_2O)_6][PtCl_6], H_2O and [Cu(H_2O)_6]^<2+> undergo 180° flips and jumping between the different Jahn-Teller configurations, respectively. A weakening of the hydrogen bond O-H…Cl upon deuteration results in a lowering of the transition temperature. (3) In [M(H_2O)_6][SiF_6], H_2O and [M(H_2O)_6]^<2+> undergo 180°flips and reorientation about the C_3 axis, respectively. The order-disorder transition is closely related to a freezing of this reorientation. (4) By elongation of [M(H_2O)_6]^<2+> along the C_3 axis, the mobility becomes higher. (5) The disorder of [Fe(H_2O)_6]^<2+> in the high-temperature phase of [Fe(H_2O)_6][SiF_6] is dynamic. Rotational modulation of [Mg(H_2O)_6]^<2+> along the C_3 axis exists in the incommensurate phase of [Mg(H2_O)_6][SiF_6]. | |||||
権利 | ||||||
権利情報 | The Japan Society for Analytical Chemistry (c) 2003 | |||||
著者版フラグ | ||||||
出版タイプ | VoR | |||||
出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||
関連URI | ||||||
識別子タイプ | URI | |||||
関連識別子 | http://ci.nii.ac.jp/naid/110002905199 | |||||
関連URI | ||||||
識別子タイプ | URI | |||||
関連識別子 | http://www.jsac.or.jp/bunka/bunsekikagaku.html | |||||
関連URI | ||||||
識別子タイプ | URI | |||||
関連識別子 | https://japanlinkcenter.org/JST.JSTAGE/bunsekikagaku/52.157 |