화학공학소재연구정보센터
Inorganic Chemistry, Vol.51, No.21, 11356-11364, 2012
Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques
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.