Theoretical study of molecular electronic excitations and optical transitions of C60

We report results on ab initio calculations of excited states of the fullerene molecule by using configuration interaction (CI) approach with singly excited determinants (SCI). We have used both the experimental geometry and the one optimized by the density functional method and worked with basis sets at the cc-pVTZ and aug-cc-pVTZ level. Contrary to the early SCI semiempirical calculations, we find that two lowest ${}^1{T}_{1u}\leftarrow {}^1{A}_g$ electron optical lines are situated at relatively high energies of ~5.8 eV (214 nm) and ~6.3 eV (197 nm). These two lines originate from two $^1 T_{1u} \leftarrow {}^1 A_g$transitions:fromHOMOto(LUMO+1)($6h_u \to 3t_{1g}$) and from (HOMO–1) to LUMO ($10h_g\to 7t_{1u}$). The lowest molecular excitation, which is the $1 ^3 T_{2g}$ level, is found at ~2.5 eV. Inclusion of doubly excited determinants (SDCI) leads only to minor corrections to this picture. We discuss possible assignment of absorption bands at energies smaller than 5.8 eV (or $\lambda$ larger than 214 nm).