Mechanisms for DNA Charge Transport

Genereux, Joseph C.; Barton, Jacqueline K.

doi:10.1021/cr900228f

Cited by 745 publications

(809 citation statements)

References 273 publications

(745 reference statements)

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“…[17][18][19][20] , and biomolecules, e.g. 21,22 , revealing a consistent picture, as described above. In contrast, experiments of the thermoelectric effect in single organic molecules have been primarily limited to situations in which off-resonant tunneling was the primary transport mechanism 2,3 .…”

Section: Introductionsupporting

confidence: 79%

Thermopower of molecular junctions: Tunneling to hopping crossover in DNA

Korol

Kilgour

Segal

2016

The Journal of Chemical Physics

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We study the electrical conductance G and the thermopower S of single-molecule junctions, and reveal signatures of different transport mechanisms: off-resonant tunneling, on-resonant coherent (ballistic) motion, and multi-step hopping. These mechanisms are identified by studying the behavior of G and S while varying molecular length and temperature. Based on a simple one-dimensional model for molecular junctions, we derive approximate expressions for the thermopower in these different regimes. Analytical results are compared to numerical simulations, performed using a variant of Büttiker's probe technique, the so-called voltagetemperature probe, which allows us to phenomenologically introduce environmentally-induced elastic and inelastic electron scattering effects, while applying both voltage and temperature biases across the junction. We further simulate the thermopower of GC-rich DNA molecules with mediating A:T blocks, and manifest the tunneling-to-hopping crossover in both the electrical conductance and the thermopower, in accord with measurements by Y. Li et al., Nature Comm. 7, 11294 (2016).

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Section: Introductionsupporting

confidence: 79%

Thermopower of molecular junctions: Tunneling to hopping crossover in DNA

Korol

Kilgour

Segal

2016

The Journal of Chemical Physics

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“…Oxidative damage in cells [1][2][3] as well as the possibility of using DNA as a biomolecular nanowire 1 have inspired studies related to the hole migration through the DNA nucleobases on a sequence of radical cation states. A major target for oxidants is guanine (G), the nucleobase with the lowest ionization potential of the four DNA bases.…”

Section: Introductionmentioning

confidence: 99%

Quantifying Environmental Effects on the Decay of Hole Transfer Couplings in Biosystems

Ramos

Pavanello

2014

J. Chem. Theory Comput.

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In the past two decades, many research groups worldwide have tried to understand and categorize simple regimes in the charge transfer of such biological systems as DNA. Theoretically speaking, the lack of exact theories for electron-nuclear dynamics on one side, and poor quality of the parameters needed by model Hamiltonians and nonadiabatic dynamics alike (such as couplings and site energies) on the other, are the two main difficulties for an appropriate description of the charge transfer phenomena. In this work, we present an application of a previously benchmarked and linear-scaling subsystem DFT method for the calculation of couplings, site energies and superexchange decay factors (β ) of several biological donor-acceptor dyads, as well as double stranded DNA oligomers comprised of up to 5 base pairs. The calculations are all-electron, and provide a clear view of the role of the environment on superexchange couplings in DNA -they follow experimental trends and confirm previous semiempirical calculations. The subsystem DFT method is proven to be an excellent tool for long-range, bridge-mediated coupling and site energy calculations of embedded molecular systems.

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“…Time resolved spectroscopy and steady state oxidative damage analyses point toward an incoherent multistep hopping mechanism, 49,60,[76][77][78][79][80][81][82] in which the hole migrates essentially by hopping between G neighboring sites, 59 with the possibility of tunnelling over short distances, when two G sites are separated by two or almost three A and/or T sites. The hopping process is in most of the cases slow, thus limiting potential applications to nano-scale electronic devices, 83,84 but since significant enhancements of HT rates have been observed both by including in the strand modified nucleobases, with a lower oxidation potentials than natural ones, or by using sequences consisting of blocks of homopurine sequences, 85,86 research in the field is still very active.…”

Section: Coherent Hole Transfer In Dnamentioning

confidence: 99%

Vibronic couplings and coherent electron transfer in bridged systems

Borrelli

Capobianco

Landi

et al. 2015

Phys. Chem. Chem. Phys.

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A discrete state approach to the dynamics of coherent electron transfer processes in bridged systems, involving three or more electronic states, is presented. The approach is based on a partition of the Hilbert space of the time independent basis functions in subspaces of increasing dimensionality, which allows for checking the convergence of the time dependent wave function.Vibronic coupling are determined by Duschinsky analysis carried out over the normal modes of the redox partners obtained at high DFT computational level.

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Mechanisms for DNA Charge Transport

Cited by 745 publications

References 273 publications

Thermopower of molecular junctions: Tunneling to hopping crossover in DNA

Thermopower of molecular junctions: Tunneling to hopping crossover in DNA

Quantifying Environmental Effects on the Decay of Hole Transfer Couplings in Biosystems

Vibronic couplings and coherent electron transfer in bridged systems

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