The Nature of the Intramolecular Charge Transfer State in Peridinin

Experimental and theoretical evidence is presented that supports the theory that the intramolecular charge transfer (ICT) state of peridinin is an evolved state formed via excited-state bond-order reversal and solvent reorganization in polar media. The ICT state evolves in <100 fs and is characterized by a large dipole moment (similar to 35 D). The charge transfer character involves a shift of electron density within the polyene chain, and it does not involve participation of molecular orbitals localized in either of the beta-rings. Charge is moved from the allenic side of the polyene into the furanic ring region and is accompanied by bond-order reversal in the central portion of the polyene chain. The electronic properties of the ICT state are generated via mixing of the 1(1)B(u)(+) ionic state and the lowest-lying 2(1)A(g)(-) covalent state. The resulting ICT state is primarily B-1(u)+-like in character and exhibits not only a large oscillator strength but an unusually large doubly excited character. In most solvents, two populations exist in equilibrium, one with a lowest-lying ICT ionic state and a second with a lowest-lying 2(1)A(g)(-) covalent state. The two populations are separated by a small barrier associated with solvent relaxation and cavity formation.