Electronic structure of C60: from the molecular to the solid state

The electronic structure of fullerides is discussed in the theoretical framework of an INDO (intermediate neglect of differential overlap) Hamiltonian defined for molecules and, in the basis of Bloch orbitals, for crystalline solids. In the C60 molecule the strength of the symmetry allowed π/σ and π*/σ* interaction is quantified by using localized molecular orbitals (MOs) as well as a so-called precanonical MO basis confined to decoupled π,π* and σ,σ* MO spaces. Consequences for the solid state electronic structure of C60 are given. The theoretical determination of the electronic transition energies in the C60 molecule in a CI (configuration interaction) calculation shows the importance of the two-electron interaction in this system. This behaviour is confirmed by Green's function calculations that are employed to derive the ionization potentials (IPs) and the electron affinity of the C60 molecule. Pair-relaxation effects in the cationic hole-states lead to significant many-body corrections to calculated ...

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