The nature of the intramolecular charge transfer state in peridinin.
The nature of the intramolecular charge transfer state in peridinin.
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DOI：
10.1016/j.bpj.2013.01.045
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发表时间：
2013-03
影响因子：
3.4
通讯作者：
Nicole L. Wagner;Jordan A. Greco;M. M. Enriquez-M.;H. Frank;R. Birge
中科院分区：
文献类型：
--
作者：
Nicole L. Wagner;Jordan A. Greco;M. M. Enriquez-M.;H. Frank;R. Birge
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 (∼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 theβ-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 "11Bu+" ionic state and the lowest-lying "21Ag–" covalent state. The resulting ICT state is primarily1Bu+-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 "21Ag–" covalent state. The two populations are separated by a small barrier associated with solvent relaxation and cavity formation.
