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AbstractAbstract
[en] Complete text of publication follows. Migration of excess charges through DNA has been a focus of considerable interest. So far most theoretical works were restricted to the description of charge motion along the well-defined static DNA structure. The two important parameters that determine the mechanism of charge transfer in DNA are site energies and charge transfer integrals. Both parameters critically depend on geometric fluctuations in DNA. I describe the magnitude of fluctuations in energies and charge transfer integrals along the donor-DNA-acceptor system. The consequences of fluctuations are discussed using stilbene-capped DNA hairpins. We exploited molecular dynamics simulations and density functional theory calculations to study the time-scale of fluctuations in the site energies and charge transfer integrals. The results were used in tight-binding calculations to evaluate the effects of structural fluctuations on hole transfer in the DNA hairpins. The injection energy barrier is higher than the average values of the charge transfer integrals. The fluctuations in site energies and charge transfer integrals are sufficiently large to lead to the domination of a fluctuation-assisted incoherent transport. The difference between the present and previous explanations is the lack of a priori assumptions about a change in the transport mechanism (from superexchange to hopping) typical for earlier works. In contrast with earlier studies, the proposed model of charge transport in fluctuating (rather than static) DNA structure provides a theoretical framework to describe the process for all bridge lengths. The results are in agreement with the full range of experimental data.
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Institute of Isotopes, Hungarian Academy of Sciences (Hungary); [63 p.]; 2009; p. 19; 26. Miller Conference on Radiation Chemistry; Keszthely (Hungary); 28 Aug - 2 Sep 2009; Available from http://www.iki.kfki.hu/miller/abstracts.shtml; 4 refs.
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