Structure and Dynamics of Metallofullerenes: New Insights

We present new results of ab initio molecular dynamics simulations of La@C(82) and Li@C(60) and the new insights gained on the endohedral chemisorption and on the dynamics. Iso- and heterocage isomers of La@C(82) are considered. The importance of the cage relaxation for a correct determination of the energetics is well established. In particular, this tends to drastically reduce the energy differences between heterocage isomers with respect to the
empty fullerenes. Calculated IR spectra are reported that clarify many of the effects of endohedral doping. Simulations of the isomerization within the same cage (82:3) show one possible dynamical path and yield the value of the free energy barrier. The Li@C(60) compound, currently at the focus of interest, is also discussed with the emphasis on its chemical and dynamical behavior compared to that of La@C(60).