Endohedral Metallofullerenes Containing Lanthanides:
A Robust Yet Simple Computational Approach
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Abstract
Endohedral metallofullerenes
(EMFs) containing lanthanides are
thoroughly analyzed using density functional theory. Our methodology,
which uses planes waves as basis functions and pseudopotentials and
takes into account the on-site Coulomb repulsion via the Hubbard-like
U parameter, is able to reproduce the electronic structure and the
main geometrical parameters for this family of compounds that presents
unpaired f electrons. In addition, the relative abundances of lanthanide
EMFs observed in chromatograms as well as the preference of a nitride
cluster for a given fullerene are properly predicted. Cluster–cage
interactions are optimal when the cluster fits perfectly within the
available hollow space of the carbon cage. Except for cerium nitride
fullerenes, f electrons do not play a significant role in the electrochemical
properties of lanthanide EMFs. If one is only interested in a qualitative
prediction of the structure, reactivity, and electronic properties,
then calculations that do not explicitly consider the unpaired f electrons
can be acceptable