Charge transfer in DNA.: Sensitivity of electronic couplings to conformational changes

被引:121
作者
Voityuk, AA [1 ]
Siriwong, K [1 ]
Rösch, N [1 ]
机构
[1] Tech Univ Munich, Inst Phys & Theoret Chem, D-85747 Garching, Germany
关键词
D O I
10.1039/b105432p
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Electronic matrix elements for hole transfer between adjacent Watson-Crick pairs in DNA have been calculated at the Hartree-Fock SCF level for various conformations of the dimer duplexes [(AT),(AT)], [(AT),(TA)], [(TA),(AT)]. Example configurations of [(TA),(TA)] have also been extracted from molecular dynamics simulations of a decamer duplex. The calculated electronic coupling is very sensitive to variations of the mutual position of the Watson-Crick pairs. The intra-strand A-A interaction is more susceptible to conformational changes titan the corresponding inter-strand interaction. The rate of charge migration as measured by the square of the electronic coupling matrix element may vary several hundred-fold in magnitude due to moderate changes of the duplex conformation. Thus, thermal fluctuations of the DNA structure have to be taken into account when one aims at a realistic description of the electron hole transfer in DNA.
引用
收藏
页码:5421 / 5425
页数:5
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