Electronic and vibrational linear and nonlinear polarizabilities of Li@C 60 and [Li@C 60 ]

Electronic and vibrational nuclear relaxation (NR) contributions to the dipole (hyper)polarizabilities of the endohedral fullerene Li@C 60 and its monovalent cation [Li@C 60 ] + are calculated at the (U)B3LYP level. Many results are new, while others differ significantly from those reported previously using more approximate methods. The properties are compared with those of the corresponding hypothetical noninteracting systems with a valence electron transferred from Li to the cage. Whereas the NR contribution to the static linear polarizabilities is small in comparison with the corresponding electronic property, the opposite is true for the static hyperpolarizabilities. A relatively small, but non‐negligible, NR contribution to the dc‐Pockels effect is obtained in the infinite frequency approximation. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011