Between superexchange and hopping: An intermediate charge-transfer mechanism in poly(A)-Poly(T) DNA hairpins

Nicolas Renaud, Yuri A. Berlin, Frederick D. Lewis, Mark A Ratner

Research output: Contribution to journalArticle

79 Citations (Scopus)

Abstract

We developed a model for hole migration along relatively short DNA hairpins with fewer that seven adenine (A):thymine (T) base pairs. The model was used to simulate hole migration along poly(A)-poly(T) sequences with a particular emphasis on the impact of partial hole localization on the different rate processes. The simulations, performed within the framework of the stochastic surrogate Hamiltonian approach, give values for the arrival rate in good agreement with experimental data. Theoretical results obtained for hairpins with fewer than three A:T base pairs suggest that hole transfer along short hairpins occurs via superexchange. This mechanism is characterized by the exponential distance dependence of the arrival rate on the donor/acceptor distance, k a ≠e-βR, with β = 0.9 Å-1. For longer systems, up to six A:T pairs, the distance dependence follows a power law ka ≠R with η = 2. Despite this seemingly clear signature of unbiased hopping, our simulations show the complete delocalization of the hole density along the entire hairpin. According to our analysis, the hole transfer along relatively long sequences may proceed through a mechanism which is distinct from both coherent single-step superexchange and incoherent multistep hopping. The criterion for the validity of this mechanism intermediate between superexchange and hopping is proposed. The impact of partial localization on the rate of hole transfer between neighboring A bases was also investigated.

Original languageEnglish
Pages (from-to)3953-3963
Number of pages11
JournalJournal of the American Chemical Society
Volume135
Issue number10
DOIs
Publication statusPublished - Mar 13 2013

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Poly T
Poly A
Base Pairing
Charge transfer
DNA
Hamiltonians
Thymine
Adenine
T-DNA
poly A-T

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Between superexchange and hopping : An intermediate charge-transfer mechanism in poly(A)-Poly(T) DNA hairpins. / Renaud, Nicolas; Berlin, Yuri A.; Lewis, Frederick D.; Ratner, Mark A.

In: Journal of the American Chemical Society, Vol. 135, No. 10, 13.03.2013, p. 3953-3963.

Research output: Contribution to journalArticle

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