Effect of Endohedral Doping in the C ₈₄ Cage on Superatom Molecular Orbitals

Exploring Superatom Molecular Orbitals (SAMOs) nearer to the Fermi level in higher fullerenes systematically provides a vital path to many molecular electronic applications. In this study, using DFT, the SAMO states of pristine and endohedrally doped C 84 derivatives with metal atoms such as Sc, Ti, V, Cr, Mn, Fe, and Co at different sites inside the cage are investigated in both their molecular and periodic forms. As anticipated, C 84 derivatives are observed with lower SAMO energy, and the lowest value of ∼1.0 eV was exhibited by the Mn‐doped derivative in both molecular and periodic forms. The charge transfer infers that the endohedrally doped metal atoms have significantly influenced the SAMO distribution in the cage. Furthermore, the band structure reveals the effect of endohedral doping on the strong dispersion of delocalized bands in the higher energy range, which interprets the overlap of the spatial wavefunctions with neighboring molecules. Hence, this study demonstrates how the nature, confinement, and energy of SAMOs near the Fermi level open new prospects for many charge transport applications in higher fullerene derivative‐based systems.