Pathways for photoinduced charge separation in DNA hairpins

被引:44
作者
Beljonne, D
Pourtois, G
Ratner, MA
Brédas, JL
机构
[1] Univ Mons, Lab Chem Novel Mat, B-7000 Mons, Belgium
[2] Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA
[3] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[4] Northwestern Univ, Mat Res Ctr, Evanston, IL 60208 USA
关键词
D O I
10.1021/ja035596f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
By means of correlated quantum-chemical calculations, we explore the chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-defined distance along the DNA strand are identified. Importantly, these involve not only the frontier molecular orbitals of the interacting donor, bridge, and acceptor units, but also deeper lying orbitals possessing both the appropriate energy and the symmetry to overlap significantly. The relative efficiency of these channels is found to be sensitive to the chemical structure of the linker, leading to falloff parameters for the charge-transfer rates ranging from similar to0.4 to similar to1.2 Angstrom(-1).
引用
收藏
页码:14510 / 14517
页数:8
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