B3Ge12: a aromatic molecular sandwich-shaped structure with short B−B single bonds coordinated by a Ge12 hexagonal prism and reinforced by σ + π double delocalised bonding patterns

• Published in: Molecular physics Vol. 118; no. 12
• Main Author: Lu, Sheng-Jie
• Format: Journal Article
• Language: English
• Published: Abingdon Taylor & Francis 17.06.2020; Taylor & Francis Ltd
• Subjects: Anions; aromaticity; bonding patterns; Bonding strength; B−Ge clusters; Capping; Cations; Chemical bonds; Chemical equilibrium; Dipole moments; Hexagons; Jellium; Molecular orbitals; Molecular structure; quantum chemical calculations; Quantum chemistry; superatom; Triangles
• ISSN: 0026-8976; 1362-3028
• DOI: 10.1080/00268976.2019.1676476

The geometrical structures and bonding properties of anionic, neutral, and cationic B 3 Ge 12 clusters are investigated by quantum chemical calculations. The lowest-lying isomer of anion is found to have a distorted B-endohedral pentagonal prism with two face-capping B atoms and two face-capping Si atoms. In particular, anion is an outstanding superatom cluster with closed-shell electronic configuration of 1S 2 1P 6 1D 10 2S 2 1F 14 2P 6 1G 18 on the principle of jellium model. Global minimum of B 3 Ge 12 neutral adopts a D 3h symmetric hexagonal prismatic structure with a B 3 triangle at the centre being parallel to the two hexagons and has strong B-B bonding interactions, being very close to the typical B−B single bond. cation has a similar structural feature with its neutral corresponding counterpart. Moreover, the nucleus-independent chemical shift (NICS), aromatic stabilisation energy (ASE), and multicenter bond index calculations suggest B 3 Ge 12 neutral to be aromatic. Furthermore, the molecular orbitals reveal that B 3 Ge 12 neutral exhibits σ plus π double bonding characters. Electrons are transferred from Ge 12 framework to B atoms in terms of natural population analysis (NPA), atoms in molecules (AIM), and atomic dipole moment corrected Hirshfeld (ADCH) population analyses.