CSi n Ge 4 −n 2+ ( n = 1–3): prospective systems containing planar tetracoordinate carbon (ptC)

• Published in: Physical chemistry chemical physics : PCCP 2022-07, Vol.24 (27), p.16701-16711
• Main Authors: Das, Prasenjit, Khatun, Maya, Anoop, Anakuthil, Chattaraj, Pratim Kumar
• Format: Article
• Language: English
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D2CP01494G

Density functional theory (DFT) based calculations have been carried out to explore the potential energy surface (PES) of CSi n Ge 4 −n 2+/+/0 ( n = 1–3) systems. The global minimum structures in the di-cationic states (1a, 1b, and 1c) contain a planar tetracoordinate carbon (ptC). For the CSi 2 Ge 2 2+ system, the second stable isomer (2b) also contains a ptC with 0.67 kcal mol −1 higher energy than that of the 1b ptC isomer. The global minima of the neutral and mono-cationic states of the designed systems are not planar. The 1a, 1b, and 1c structures follow the 18 valence electron rule. The relative energies of the low-lying isomers of CSiGe 3 2+ , CSi 2 Ge 2 2+ , and CSi 3 Ge 2+ systems with respect to the global minima were calculated using the CCSD(T)/aug-cc-pVTZ method . Ab initio molecular dynamics simulations for 50 ps time indicate that all the global minimum structures (1a, 1b, and 1c) are kinetically stable at 300 K and 500 K temperatures. The natural bond orbital (NBO) analysis suggests strong σ-acceptance of the ptC from the four surrounding atoms and simultaneously π-donation occurs from the ptC center. The nucleus independent chemical shift (NICS) showed σ/π-dual aromaticity. We hope that the designed di-cationic systems may be viable in the gas phase.