Distance dependence of hole transfer rates from G radical cations to GGG traps in DNA

Abstract

Relative reaction rates for hole transfer between G radical cations and GGG triplets in DNA, through different bridges of varying lengths, are numerically calculated and the obtained results are compared with corresponding experimental observations [Giese et al., 2001, Nature, 412, 318; Angew. Chem., Int. Ed., 1999, 38, 996]. Hole donors and acceptors are separated either by (T–A)_n bridges or by N repeated barriers consisting of (T–A,T–A) double base-pairs which are connected through single G–C base-pairs. In the former case, hole transfer rates show a strong exponential decrease with the length of the bridge for short bridges, while a switching to weak distance dependence has been observed for longer bridges. In the latter case, a power law seems to better describe the distance dependence of charge transfer rates. All these experimental observations are qualitatively reproduced by our simulations without any adjustable parameter, considering only tunneling as the charge transfer mechanism. Physical insights into the mechanism providing the switching behavior in the case of (T–A)_n bridges are presented through an analysis of the eigenfunctions of the system.