Structural and electronic properties of la@c82.

The structural and electronic properties of the La@C(82) fullerene have been investigated by means of the Car-Parrinello method, which is based on the local density approximation of the density functional theory. The topological arrangement of the C(82) cage was assumed to be a C(3v) symmetry isomer. Three configurations were considered, one with the lanthanum atom at the center of the cluster, one with it along the threefold axis, and one with it at a low-symmetry, highly coordinated site. The structure was fully relaxed and it was found that the last of these configurations is energetically preferred. In this position, the lanthanum atom is nearly in a La(3+) state and the unpaired electron is somewhat delocalized on the cage, in agreement with available experimental data. This arrangement suggests that the chemical shifts of the 5s and 5p lanthanum states can be used as a structural probe and as a way of further validating this picture. It is argued that this conclusion is not affected by the assumed fullerene structure.