Pavlyuk Volodymyr, Dmytriv Grygoriy, Tarasiuk Ivan, Chumak Ihor, Ehrenberg Helmut
Department of Inorganic Chemistry, Ivan Franko Lviv National University, Kyryla and Mefodiya str. 6, 79005 Lviv, Ukraine.
Acta Crystallogr C. 2011 Dec;67(Pt 12):i59-62. doi: 10.1107/S0108270111048566. Epub 2011 Nov 26.
New ternary dodecalithium dodecacopper tetradecaaluminium, Li(12)Cu(12.60)Al(14.37) (trigonal, R ̅3m, hR39), crystallizes as a new structure type and belongs to the structural family that derives from binary Laves phases. The Li atoms are enclosed in 15- and 16-vertex and the Al3 atom in 14-vertex pseudo-Frank-Kasper polyhedra. The polyhedra around the statistical mixtures of (Cu,Al)1 and (Al,Cu)2 are distorted icosahedra. The electronic structure was calculated by the TB-LMTO-ASA (tight-binding linear muffin-tin orbital atomic spheres approximation) method. The electron localization function, which indicates bond formation, is mostly located at the Al atoms. Thus, Al-Al bonding is much stronger than Li-Al or Cu-Al bonding. This indicates that, besides metallic bonding which is dominant in this compound, weak covalent Al-Al interactions also exist.
新型三元十二锂十二铜十四铝化合物Li(12)Cu(12.60)Al(14.37)(三方晶系,R ̅3m,hR39)以一种新的结构类型结晶,属于源自二元Laves相的结构家族。锂原子被包含在15和16顶点的多面体中,铝原子被包含在14顶点的伪Frank-Kasper多面体中。(Cu,Al)1和(Al,Cu)2的统计混合物周围的多面体是扭曲的二十面体。通过TB-LMTO-ASA(紧束缚线性 muffin-tin轨道原子球近似)方法计算了电子结构。表明键形成的电子定域函数主要位于铝原子处。因此,Al-Al键比Li-Al或Cu-Al键强得多。这表明,除了在该化合物中占主导的金属键外,还存在弱的共价Al-Al相互作用。