Dynamical fluxionality, multiplicity of geometrical forms, and electronic properties of anionic, neutral, and cationic TanSi12 (n = 1–3) clusters: quantum chemical calculations

• Published in: Molecular physics Vol. 118; no. 12
• Main Author: Sheng-Jie, Lu
• Format: Journal Article
• Language: English
• Published: Abingdon Taylor & Francis Ltd 17.06.2020
• Subjects: Bonding strength; Cations; Chemical bonds; Clusters; Isomers; Mathematical analysis; Molecular orbitals; Quantum chemistry; Vertical penetration
• ISSN: 0026-8976; 1362-3028
• DOI: 10.1080/00268976.2019.1682209

The dynamical fluxionality, multiplicity of geometrical forms, and electronic properties of anionic, neutral, and cationic TanSi12 (n = 1–3) clusters are studied by quantum chemical calculations. The results show that (n = 1–3) clusters are dominated by prism-based geometries. Impressively, neutral and cationic TanSi12 (n = 1–3) clusters have multiple geometrical forms and their low-lying isomers exhibit dynamical fluxionality. is a D6h symmetric Ta-endohedral Si12 hexagonal prism with highly electronically stability because of satisfying the 18-electrons rule, and having a closing-shell electronic configuration with a large HOMO–LUMO gap of 2.81 eV and delocalised Ta-Si12 ligand interactions. clusters have a C2v symmetric Ta-endohedral bicapped pentagonal prism. In , a Si5 pentagonal ring and a Si7 heptagonal ring are bridged by the Ta−Ta bonding axis, which is perpendicular to the Si5 and Si7 frameworks. adopts a bicapped hexagonal antiprism with one Ta atom encapsulated into the TaSi11 hexagonal antiprism, whereas neutral and cationic Ta3Si12 hold a TaSi5 hexagon and a Si7 heptagon penetrated by the vertical Ta−Ta bond. The Ta atoms in (n = 2–3) clusters have strong bonding interactions and the charges are transferred from the Si12 frameworks to the Ta atoms.