HOMO-LUMO transitions in solvated and crystalline picene

The optical properties of picene at ambient conditions have been investigated through the measurement of UV/Vis absorption and fluorescence spectra and of excitation profiles, using one- and two-photon excitation, in solution and in the crystal phase. For solvated picene an assignment of the vibronic structure of the transitions to the four lowest-energy excited singlet states (S(1)-S(4)) has been obtained from the absorption data, and the vibronic structure of the fluorescence spectra has been assigned. The absorption and fluorescence spectra of the solid phase can be interpreted according to the single molecule analysis. Nevertheless, the strong increase of the optical density in the spectral region of the lowest HOMO-LUMO transitions and the frequency shift of absorption and fluorescence bands may be explained by a mixing of the states of adjacent molecules in the crystal. Moreover, peculiar emission features depending on the crystal dimensions (10(-1) to 10(2) μm) are observed.