Mikhailov Oleg V, Chachkov Denis V
Department of Analytical Chemistry, Certification and Quality Management, Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia.
Kazan Department of Joint Supercomputer Center of Russian Academy of Sciences-Branch of Federal Scientific Center "Scientific Research Institute for System Analysis of the RAS", Lobachevskii Street 2/31, 420111 Kazan, Russia.
Materials (Basel). 2021 Nov 12;14(22):6836. doi: 10.3390/ma14226836.
Quantum-chemical calculation of most important parameters of molecular and electronic structures of tetra-nuclear () metal clusters having AlM composition, where M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or Zn (bond lengths, bond and torsion angles), and HOMO and LUMO of these compounds by means of DFT OPBE/QZVP method, have been carried out. It has been found that, for each of these metal clusters, an existence of rather large amount of structural isomers different substantially in their total energy, occurs. It has been noticed that molecular structures of metal clusters of the given type differ significantly between them in terms of geometric parameters, as well as in geometric form, wherein the most stable modifications of metal clusters considered are similar between themselves in geometric form. In addition, the standard thermodynamic parameters of formation of metal clusters considered here, and namely standard enthalpy Δ(298 K), entropy S(298 K), and Gibbs' energy Δ(298 K) of formation for these metal clusters, were calculated.
采用DFT OPBE/QZVP方法，对具有AlM组成（其中M = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu或Zn）的四核金属簇的分子和电子结构的最重要参数（键长、键角和扭转角）以及这些化合物的最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）进行了量子化学计算。研究发现，对于这些金属簇中的每一个，都存在相当数量的结构异构体，它们的总能量有很大差异。已经注意到，给定类型的金属簇的分子结构在几何参数以及几何形状方面彼此有显著差异，其中所考虑的金属簇的最稳定构型在几何形状上彼此相似。此外，还计算了这里所考虑的金属簇形成的标准热力学参数，即这些金属簇形成的标准焓Δ(298 K)、熵S(298 K)和吉布斯自由能Δ(298 K)。
