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The evolution of the electronic properties of a thin film of copper phthalocyanine deposited on Al(100) and progressively intercalated with rubidium atoms was followed by photoemission and X-ray absorption spectroscopies. Electron donation from the Rb atoms to the C32H16N8Cu molecules results in the lifting of the degeneracy in the eg ligand-derived molecular orbital and the lowering of the molecular symmetry. For Rb∼2C32H16N8Cu, spectral evidence indicates that both donated electrons reside in the first split-off eg-derived level, thus creating an electronic inequivalence between the C atoms in the benzene rings. For higher Rb concentrations, a reduction of the Cu oxidation state is observed, together with a new Cu-derived state in valence-band photoemission spectra, testifying to the filling of the b1g orbital. Thus, even though b1g is the lowest unoccupied orbital of the neutral molecule, in the film, the Cu-derived b1g-derived states are occupied only after a partial filling of the eg-derived band has...

Electronic Properties and Orbital-Filling Mechanism in Rb-Intercalated Copper Phthalocyanine