A systematic investigation on the structure, energy, aromaticity, and stability of substituted X₅Y₅C₁₀ nanocages (X=B, Al, Ga, and Y=N, P, As)

Abstract

Density functional theory (DFT) calculations are applied to devise highly doped Cs symmetry X5Y5C10 (X=B, Al, Ga, and Y=N, P, As) heterofullerenes where the substituents are completely linked to each other by means of strong X–Y bonds in equatorial position. The structural stabilities, geometry, and electronic properties of these systems are compared and contrasted at the B3LYP/AUG‐cc‐pVTZ, B3LYP/6‐311++G**, B3LYP/6‐311+G*, and B3PW91/6‐311+G* computational levels. Vibrational frequency analysis confirms that all of these nonsegregated nanocages are real minima. B5N5C10 immerges with the highest HOMO‐LUMO energy separation (2.18 eV). Hence, it is predicted to be the most chemically stable against electronic excitation. In contrast, Al5N5C10 that appears with the narrowest band gaps (1.13 eV), the highest conductivity, and the most charge transfer is the best candidate for hydrogen storage. Assuming the heat of atomization, B5N5C10 is expected to be the most thermodynamically stable heterofullerene. The nucleus‐independent chemical shift calculations at cage center and 1 Å above the cage center are exhibited the most negative value of NICS (0), NICS (1) (−28.08 and −37.80 ppm, respectively) and the most aromaticity for Ga5N5C10 heterofullerene.

A DFT study on effective detection of ClCN gas by functionalized, decorated, and doped nanocone strategies

“…The CNC molecule was functionalized with pyridinol (CNC/Pyr) and pyridinol oxide (CNC/ PyrO), decorated with metals (M = B, Al, and Ga) (CNC/M), and doped with the same metals (M = B, Al, and Ga) (CNC-M) with and without the ClCN molecule. 28 The B3LYP functional has been used for theoretical studies in previous letters, [29][30][31] and also 6-31G(d) basis set has been used in a similar work. 32 Aer the optimization and obtained all considered congurations, full optimization using M06-2X/6-311G(d) are performed for favorable congurations (CNC-Al, CNC-Ga, S21 and S22 congurations) to obtain more accurate results.…”

“…Several reports exist on the doping elements of the third group in the structure of nanocarbon materials to increase their reactivity toward chemicals. 27,31,32,[49][50][51] Previous research has demonstrated that the introduction of B, Al, and Ga ions into carbon nanostructures has a signicant effect on their electronic properties. Through the doping processes of these elements, the electrical conductivity, optical properties, and surface reactivity of carbon nanostructures can be modied, leading to new and improved applications.…”

Fluoromaticity: The Molecular Orbital Contributions of Fluorine Substituents to the π-Systems of Aromatic Rings

“…Augmented basis sets allow for a more accurate treatment of long-range interactions like those seen in extensively conjugated systems. The B3LYP/AUG-cc-pVTZ model chemistry has been used extensively in recent years to model the aromaticity and its causes. − Geometries optimized with DFT were verified with frequency analysis at the same level of theory as the optimization to assure no imaginary vibrational frequencies. Orbital population analysis was also conducted at the same level of theory.…”

Exploring porphyrins induced carbon nanocone TM-PICNC (TM = Sc2+, Ti2+, V2+, Cr2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) as a highly sensitive sensor for CO2 gas detection in presence O2 and H2O molecules: a computational study

“…All calculations were conducted at the DFT level using hybrid density functional (B3LYP) ( Becke, 1993 ) and 6-31G(d) basis set( Ochterski et al, 1996 ) in the gas phase with the GAMESS software ( Schmidt et al, 1993 ). Previous studies ( Baei, 2012 ; Hizhnyi et al, 2017 ; Soleimani-Amiri, 2017 ) utilized the B3LYP functional for theoretical investigations, while a similar work ( Baei et al, 2012 ) employed the 6–31 g(d) basis set. After the full optimization and obtained all considered configurations, single point calculations B3LYP/CC-PVTZ level of theory ( Dunning Jr, 1989 ; Kendall et al, 1992 ) are performed for favorable configurations (CNC, PICNC and V-PICN configurations) to obtain more accurate results.…”