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

Abstract

AbstractDensity 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.