Osman, Hussien H.Bobev, Svilen2022-04-252022-04-252021-12-23Osman, Hussien H., and Svilen Bobev. “Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li15Ge4 vs Li14ZnGe4.” European Journal of Inorganic Chemistry 2022, no. 4 (February 8, 2022). https://doi.org/10.1002/ejic.202100901.1099-0682https://udspace.udel.edu/handle/19716/30812This is the peer reviewed version of the following article: Osman, Hussien H., and Svilen Bobev. “Experimental and Theoretical Study on the Substitution Patterns in Lithium Germanides: The Case of Li15Ge4 vs Li14ZnGe4.” European Journal of Inorganic Chemistry 2022, no. 4 (February 8, 2022). https://doi.org/10.1002/ejic.202100901, which has been published in final form at https://doi.org/10.1002/ejic.202100901. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited. This article will be embargoed until 12/23/2022.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 group /43d 3d (no. 220) with unit cell parameter of 10.695(1) Å. The crystal structure refinements show that the parent Li15Ge4 structure 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 Li15Ge4 structure 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.en-USGermanidesLithiumSolid-state synthesisStructure elucidationZintl phasesArticle