DECAY OF S1-STATE OF PERIDININ IN MEDIA OF DIFFERENT POLARITY AND CONFORMERS
Abstract
Theory of nonradiative transitions based on the model of the orientation broadening of electronic levels has been used to interpret the known data for the medium polarity effect on the lifetime of the S1(Ag−) state of peridinin. The findings allow assuming that the molecules of pigment heavily interact with the internal electric field produced by environment. In consequence of this, peridinin at the excited S1(Ag−) state exists in the form of different conformers I and II with permanent dipole moments of 40.7 and 42.8 D, respectively. Their structure is distinguished by turning the epoxycyclohexane ring relative to the polyene chain through about 180°. Conformer I is dominant in nonpolar and low polar media and is at the intramolecular charge transfer state S1(Ag−/ICT), − whereas conformer II exists in polar media and, as suggested, belongs to the charge separated state S1(Ag−/ICT).
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