Structures, stabilities, and electronic properties of fullerene C36 with endohedral atomic Sc, Y, and La: A dispersion‐corrected DFT study

• Published in: International journal of quantum chemistry 2017-03, Vol.117 (6), p.n/a
• Main Authors: Miralrio, Alan, Enrique Sansores, Luis
• Format: Article
• Language: English
• Subjects: C36 fullerene; Chemistry; density functional theory calculation; dispersion‐corrected; electronic structure; endohedral fullerenes; Physical chemistry; Quantum physics
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.25335

The M@C36 compounds form a family of small endohedral metallofullerenes. Recently, these have been detected as the smallest endohedral compounds formed with Sc, Y, and La. For the first time, these compounds are studied theoretically. Calculations obtained at the dispersion‐corrected DFT level PBE‐D3(BJ)/def2‐TZVP agree admirably with experimental results. The zero‐point energy corrected binding energies can explain the lower abundance of La@C36 in comparison with Sc@C36 and Y@C36. Their small HOMO‐LUMO gaps denote high reactivity. The bond between Y and Sc with the cage is mostly covalent. In contrast, La is located at the fullerene's center with an ionic interaction; all metals transferred charge to the cage. Furthermore, La@C36 was found in doublet state and the others preferred the quartet state. To conclude, according to the analysis of aromaticity performed by the NICS(0)iso index, the insertion of none of these metals increase the aromaticity. The M@C36 (M = Sc, Y, and La) are part of a family of experimentally obtained endohedral metallofullerenes. For the first time, these compounds are studied theoretically. Results were obtained at the dispersion‐corrected DFT level PBE‐D3(BJ)/def2‐TZVP. Binding energies explain the abundances obtained experimentally. Their small HOMO‐LUMO gaps denote high reactivity. The bond between Y and Sc with the cage is mostly covalent and ionic in the case of La. Their stabilities are not increased by aromaticity.