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Ln(4)FeGa(12)(Ln = Y、Tb、Dy、Ho 和 Er)的晶体生长、输运以及结构和磁性性质。

Crystal growth, transport, and the structural and magnetic properties of Ln(4)FeGa(12) with Ln = Y, Tb, Dy, Ho, and Er.

机构信息

Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, Louisiana 70803, USA.

出版信息

Inorg Chem. 2010 Jan 18;49(2):445-56. doi: 10.1021/ic9013202.

Abstract

Ln(4)FeGa(12), where Ln is Y, Tb, Dy, Ho, and Er, prepared by flux growth, crystallize with the cubic Y(4)PdGa(12) structure with the Im3m space group and with a = 8.5650(4), 8.5610(4), 8.5350(3), 8.5080(3), and 8.4760(3) A, respectively. The crystal structure consists of an iron-gallium octahedra and face-sharing rare-earth cuboctahedra of the Au(3)Cu type. Er(4)Fe(0.67)Ga(12) is iron-deficient, leading to a distortion of the octahedral and cuboctahedral environments due to the splitting of the Ga2 site into Ga2 and Ga3 sites. Further, interstitial octahedral sites that are unoccupied in Ln(4)FeGa(12) (Ln = Y, Tb, Dy, and Ho) are partially occupied by Fe2. Y(4)FeGa(12) exhibits weak itinerant ferromagnetism below 36 K. In contrast, Tb(4)FeGa(12), Dy(4)FeGa(12), Ho(4)FeGa(12), and Er(4)Fe(0.67)Ga(12) order antiferromagnetically with maxima in the molar magnetic susceptibilities at 26, 18.5, 9, and 6 K. All of the compounds exhibit metallic electric resistivity, and their iron-57 Mossbauer spectra, obtained between 4.2 and 295 K, exhibit a single-line absorption with a 4.2 K isomer shift of ca. 0.50 mm/s, a shift that is characteristic of iron in an iron-gallium intermetallic compound. A small but significant broadening in the spectral absorption line width is observed for Y(4)FeGa(12) below 40 K and results from the small hyperfine field arising from its spin-polarized itinerant electrons.

摘要

Ln(4)FeGa(12)(Ln 为 Y、Tb、Dy、Ho 和 Er)通过熔剂生长法制备,结晶为立方 Y(4)PdGa(12)结构,空间群为 Im3m,晶胞参数分别为 a = 8.5650(4)、8.5610(4)、8.5350(3)、8.5080(3)和 8.4760(3)Å。晶体结构由铁-镓八面体和 Au(3)Cu 型共角的稀土立方体组成。Er(4)Fe(0.67)Ga(12) 是铁贫化的,由于 Ga2 位分裂为 Ga2 和 Ga3 位,导致八面体和立方体环境发生扭曲。此外,Ln(4)FeGa(12)(Ln = Y、Tb、Dy 和 Ho)中未占据的间隙八面体位部分被 Fe2 占据。Y(4)FeGa(12)在 36 K 以下表现出弱的巡游铁磁性。相比之下,Tb(4)FeGa(12)、Dy(4)FeGa(12)、Ho(4)FeGa(12)和 Er(4)Fe(0.67)Ga(12)则反铁磁有序,摩尔磁化率最大值出现在 26、18.5、9 和 6 K。所有化合物均表现出金属电导率,其铁-57 穆斯堡尔谱在 4.2 至 295 K 之间,呈现单一线吸收,4.2 K 处的同晶位移约为 0.50 mm/s,这是铁-镓金属间化合物中铁的特征。在 40 K 以下,Y(4)FeGa(12)的光谱吸收线宽略有增大,这是由于其自旋极化巡游电子产生的小超精细场所致。

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