Abstract
The ultraviolet photoelectron spectra of solid iodine have been measured. The observed spectral features show a large deviation from a one-to-one correspondence with the gas phase spectrum. These results are examined by an extended Hückel band calculation, which indicates that this deviation is caused by the effect of a strong intermolecular interaction on the electronic structure, namely the formation of broad bands (0.7 to 2.0 eV). The characters of the observed spectral features are assigned by the calculated density of states. The energy gap is estimated to be 1.6 eV from the observed energy difference between the Fermi level and the top of valence bands (5.52 and 6.34 eV relative to the vacuum level, respectively), by assuming that iodine is an intrinsic semiconductor. The large decrease of ionization threshold energy (2.92 eV) from the gas to the solid state is also discussed.
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