Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques

被引：28
作者：
Steinberg, Simon [1 ]
Brgoch, Jakoah [2 ]
Miller, Gordon J. [2 ]
Meyer, Gerd [1 ]
机构：
[1] Univ Cologne, Dept Inorgan Chem, D-50939 Cologne, Germany
[2] Iowa State Univ, Dept Chem, Ames, IA 50011 USA
来源：
INORGANIC CHEMISTRY | 2012年 / 51卷 / 21期
基金：
美国国家科学基金会;
关键词：
HAMILTON POPULATIONS; CLUSTER HALIDES; CRYSTAL; ATOMS; MN; FE;
D O I：
10.1021/ic300838a
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The structures of two new cubic {TnLa(3)}Br-3 (Tn = Ru, Ir; I4(1)32, Z = 8; Tn = Ru: a = 12.1247(16) angstrom, v = 1782.4(4) angstrom(3); Tn = Ir: a = 12.1738(19) angstrom, V = 1804.2(5) angstrom(3)) compounds belonging to a family of reduced rare-earth metal halides were determined by single-crystal X-ray diffraction. Interestingly, the isoelectronic compound {RuLa3}I-3 crystallizes in the monoclinic modification of the {TnR(3)}X-3 family, while {IrLa3}I-3 was found to be isomorphous with cubic {PtPr3}I-3. Using electronic structure calculations, a pseudogap was identified at the Fermi level of {IrLa3}Br-3 in the new cubic structure. Additionally, the structure attempts to optimize (chemical) bonding as determined through the crystal orbital Hamilton populations (COHP) curves. The Fermi level of the isostructural {RuLa3}Br-3 falls below the pseudogap, yet the cubic structure is still formed. In this context, a close inspection of the distinct bond frequencies reveals the subtleness of the structure determining factors.
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页码：11356 / 11364
页数：9
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