The metallofullerene Tm@C 82 : isomer-selective electronic structure

Abstract

using photoemission and electron energy-loss spectroscopy in transmission. In particular, the impact of the isomer symmetry of the C82 cage (Cs or C3v) on the electronic structure and on the optical properties is analysed in detail. For both isomers, combined XPS and XAS measurements of the Tm 4f and 4d states offer conclusive proof of a divalent encaged Tm ion. No significant change of the valence of the rare earth ion upon changes in the cage symmetry is observed. From the C 1s excitation spectra we find a more pronounced LUMO for the C3v(8) isomer, as is expected for the higher symmetry of the cage. Additional information about the optical properties was obtained from the low-energy loss function. With use of a Kramers–Kronig analysis, the dielectric function, e, and the optical conductivity, σ, have been derived. e(0) and the onset of the spectral weight are found to be 7.7 [12.8] and 0.6 eV [0.8 eV] for the Cs(6) {C3v(8)} isomer, respectively.