Journal
BIOPHYSICAL JOURNAL
Volume 104, Issue 6, Pages 1314-1325Publisher
CELL PRESS
DOI: 10.1016/j.bpj.2013.01.045
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Funding
- National Institutes of Health [GM-34548]
- National Science Foundation [EMT-0829916, MCB-0913022]
- Harold S. Schwenk Sr. Distinguished Chair in Chemistry
- University of Connecticut Research Foundation
- Div Of Molecular and Cellular Bioscience
- Direct For Biological Sciences [0913022] Funding Source: National Science Foundation
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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.
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