Electronic structure of C84 and KxC84: Comparison to C60 and graphite

X ray photoemission spectra show ～10 valence band features in C₆₀ and C₈₄ films, although they are less distinct in C₈₄ because of the increased number of valence electrons and the decreased molecular symmetry. The presence of inequivalent carbon atoms in C₈₄ is reflected by the fact that the C 1s main line is ～0.2 eV wider than in C₆₀. The C 1s satellite region of C₈₄ exhibits four features within 15 eV of the main line and shows that the HOMO-LUMO π-π* excitation energy of C₈₄ is ～0.5 eV smaller than in C₆₀. Potassium 2p spectra for K-doped C₈₄ films suggest the formation of a phase with composition K₃C₈₄ with two spectroscopically-distinguishable K sites. A new spectral feature emerges when the K content is increased beyond K₃C₈₄, suggesting a phase transition and a saturated composition of K₆C₈₄, as for K_xC₆₀. These similarities are intriguing since K_xC₈₄ is insulating for all x while K₃C₆₀ is metallic and superconducting.