Electronic structure of predicted endohedral fullerenes An@C40 (An = Th–Md)

The geometry optimization of the neutral molecules An@C40 (An = Th–Md) was carried out using the DFT based DMol3 method. For the calculations of electronic structure of these complexes we used the fully relativistic discrete variational method (RDV). The systems containing Th, Pa, U and Np have considerable energetic stability, which is noticeably greater than that of corresponding exohedral and “networked” complexes. The clusters containing actinide atom from Pu to Fm are also more stable than empty C40 cage. It was found, that the 5f-orbitals contribution to chemical bonding is noticeably less than that of the 6d-states even for the complexes at the beginning of An@C40 row. The effective charges on the atoms were calculated using integral scheme incorporated in RDV and Hirshfeld procedure of DMol3.