Quantum-Chemical Consideration of Al2M2 Tetranuclear Metal Clusters (M-3 d-Element): Molecular/Electronic Structures and Thermodynamics

Oleg V Mikhailov; Denis V Chachkov

doi:10.3390/ma14226836

Quantum-Chemical Consideration of Al₂M₂ Tetranuclear Metal Clusters (M-3 d-Element): Molecular/Electronic Structures and Thermodynamics

Materials (Basel). 2021 Nov 12;14(22):6836. doi: 10.3390/ma14226836.

Authors

Oleg V Mikhailov¹, Denis V Chachkov²

Affiliations

¹ Department of Analytical Chemistry, Certification and Quality Management, Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia.
² 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.

Abstract

Quantum-chemical calculation of most important parameters of molecular and electronic structures of tetra-nuclear (pd) metal clusters having Al₂M₂ 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_fH⁰(298 K), entropy S_f⁰(298 K), and Gibbs' energy Δ_fG⁰(298 K) of formation for these metal clusters, were calculated.

Keywords: DFT method; aluminum; chromium; cobalt; copper; iron; manganese; metal cluster; molecular structure; nickel; scandium; thermodynamic parameters; titanium; vanadium; zinc.