Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li 15 Ge 4 vs Li 14 ZnGe 4
Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li 15 Ge 4 vs Li 14 ZnGe 4
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锗化锂中取代模式的实验和理论研究：以Li 15 Ge 4 与Li 14 ZnGe 4 为例
DOI：
10.1002/ejic.202100901
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发表时间：
2021
影响因子：
2.3
通讯作者：
Bobev, Svilen
中科院分区：
文献类型：
--
作者：
Osman, Hussien H.;Bobev, Svilen
通过高温固相反应合成了一种新的三元锂锌锗化合物Li13.83Zn1.17（2）Ge 4。晶体结构通过单晶X射线衍射方法确定。新相在体心立方空间群I3 d（编号220）中结晶，晶胞参数为10.695（1）Ω。晶体结构的改进表明，母体Li 15 Ge 4结构通过元素Zn的富一电子原子随机取代Li原子而稳定为Li 15 − xZnxGe 4（x <$1），从而增加了价电子的数量，导致电子更稳定的系统。通过理论和实验研究了Li_（15）Ge_（4）结构中的取代效应，证实了Zn原子在该结构中只占据Li的两个晶位中的一个.从实验结果建立的优选取代模式的支持DFT电子结构计算，这也探讨了微妙的化学键和标题化合物的电子性质。
A new ternary lithium zinc germanide, Li13.83Zn1.17(2)Ge4, was synthesized by a high‐temperature solid state reaction of the respective elements. The crystal structure was determined by single‐crystal X‐ray diffraction methods. The new phase crystallizes in the body‐centered cubic space groupI3d(no. 220) with unit cell parameter of 10.695(1) Å. The crystal structure refinements show that the parent Li15Ge4structure is stabilized as Li15−xZnxGe4(x≈1) via random substitution of Li atoms by the one‐electron‐richer atoms of the element Zn, by virtue of which the number of valence electrons increases, leading to a more electronically stable system. The substitution effects in the parent Li15Ge4structure were investigated through both theory and experiment, which confirm that the Zn atoms in this structure prefer to occupy only one of the two available crystallographic sites for Li. The preferred substitution pattern established from experimental results is supported by DFT electronic structure calculations, which also explore the subtleties of the chemical bonding and the electronic properties of the title compounds.