| Abstract
| - The results of a theoretical study of the ground state, 1Ag, and of the lowest 1Bu states of trans-stilbene arepresented. The vertical and adiabatic excitation energies of the lowest 1Bu states have been computed usingmulticonfigurational SCF theory, followed by second-order perturbation theory. It is shown that the two lowestexcited states are separated by a small energy gap in the Franck−Condon region. They are the 11Bu,characterized by the HOMO→LUMO single excitation substantially localized on the ethylenic moiety, andthe 21Bu, formed by a combination of one electron excitations localized mainly on the benzene rings. Themost intense transition is found to be the lowest in energy when the interaction between different states isincluded at the level of second-order perturbation theory. The vibronic structure of emission and absorptionspectra of the two lowest 1Bu states have been determined within the Franck−Condon approximation. Thespectrum calculated for the 11Bu state agrees with the experimental spectrum, while the low intensity bandcomputed for the 21Bu state has no experimental counterpart. It is concluded that this band is buried in thestrong 11Bu absorption and therefore not observed.
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