title: Impact of a single base pair substitution on the charge transfer rate along short DNA hairpins.
abstract: Numerical studies of hole migration along short DNA hairpins were performed with a particular emphasis on the variations of the rate and quantum yield of the charge separation process with the location of a single guanine:cytosine (G:C) base pair. Our calculations show that the hole arrival rate increases as the position of the guanine:cytosine base pair shifts from the beginning to the end of the sequence. Although these results are in agreement with recent experimental findings, the mechanism governing the charge migration along these sequences is revisited here. Instead of the phenomenological two-step hopping mechanism via the guanine base, the charge propagation occurs through a delocalization of the hole density along the base pair stack. Furthermore, the variations of the charge transfer with the position of the guanine base are explained by the impact of the base pair substitutions on the delocalized conduction channels.
authors: Department of Chemistry, Northwestern University, Evanston, IL 60208-3113.
authors: Nicolas
authors: N
authors: Renaud
authors: Yuri A
authors: YA
authors: Berlin
authors: Mark A
authors: MA
authors: Ratner
mesh_terms: D020029:Base Pairing; D004247:DNA / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D009690:Nucleic Acid Conformation; D055672:Static Electricity; D013269:Stochastic Processes
chemical_list: D004247:DNA
keywords: photoinduced hole transfer; quantum filling; stochastic surrogate Hamiltonian
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