Univeristy of Regensburg , 93053 Regensburg , Germany.
Department of Chemistry , Lomonosov Moscow State University , 119991 Moscow , Russia.
Inorg Chem. 2019 Mar 4;58(5):3435-3443. doi: 10.1021/acs.inorgchem.8b03554. Epub 2019 Feb 21.
Four new transition metal-free pnictide representatives of the LaOAgS structure type were predicted by DFT calculations and found in the BaFMgPn (Pn = P, As, Sb and Bi) family. The compounds adopt the tetragonal space group P4 /nmm with the unit cell parameters a/ c 4.3097(1) Å/9.5032(1) Å, 4.3855(1) Å/9.5918(1) Å, 4.5733(1) Å/9.8184(1) Å, and 4.6359(1) Å/9.8599(1) Å, respectively. According to the DFT calculations, these new compounds are semiconductors with band gaps steadily decreasing from Pn = P ( ca. 2 eV) to Pn = Bi ( ca. 1 eV). The corresponding strontium fluoride and rare-earth oxide analogs are unlikely to exist and have not been observed yet. The trends of the stability within 1111 and structurally and/or chemically related compounds based on a combined consideration of geometry and DFT calculations are discussed.
通过 DFT 计算预测了 LaOAgS 结构类型的四种新的过渡金属自由磷化物代表，并在 BaFMgPn（Pn = P、As、Sb 和 Bi）家族中发现了它们。这些化合物采用四方空间群 P4/nmm，其晶胞参数分别为 a/ c 4.3097(1) Å/9.5032(1) Å、4.3855(1) Å/9.5918(1) Å、4.5733(1) Å/9.8184(1) Å和 4.6359(1) Å/9.8599(1) Å。根据 DFT 计算，这些新化合物是半导体，带隙从 Pn = P（约 2 eV）稳定地减小到 Pn = Bi（约 1 eV）。相应的氟化锶和稀土氧化物类似物不太可能存在，尚未观察到。讨论了基于几何形状和 DFT 计算的综合考虑的 1111 内稳定性以及结构和/或化学相关化合物的趋势。
