Combined density functional theory and Landauer approach for hole transfer in DNA along classical molecular dynamics trajectories

Research output: Contribution to journalReview articleContributedpeer-review

Contributors

Abstract

We investigate in detail the charge transport characteristics of DNA wires with various sequences and lengths in the presence of solvent. Our approach combines large-scale quantum/classical molecular dynamics (MD) simulations with transport calculations based on Landauer theory. The quantum mechanical transmission function of the wire is calculated along MD trajectories and thus encodes the influence of dynamical disorder arising from the environment (water, backbone, counterions) and from the internal base dynamics. We show that the correlated fluctuations of the base pair dynamics are crucial in determining the transport properties of the wire and that the effect of fluctuations can be quite different for sequences with low and high static disorders (differences in base ionization potentials). As a result, in structures with high static disorder as is the case of the studied Dickerson dodecamer, the weight of high-transmissive structures increases due to dynamical fluctuations and so does the calculated average transmission. Our analysis further supports the basic intuition of charge-transfer active conformations as proposed by Barton [J. Am. Chem. Soc. 126, 11471 (2004)]. However, not DNA conformations with good stacking contacts leading to large interbase hopping values are necessarily the most important, but rather those where the average fluctuation of ionization potentials along the base stack is small. The reason behind this is that the ensemble of conformations leads to average electronic couplings, which are large enough for sufficient transmission. On the other hand, the alignment of onsite energies is the critical parameter which gates the charge transport.

Details

Original languageEnglish
Article number215104
Number of pages14
JournalJournal of Chemical Physics
Volume130
Issue number21
Publication statusPublished - 7 Jun 2009
Peer-reviewedYes

External IDs

Scopus 67249157834
WOS 000266674400055
PubMed 19508103
ORCID /0000-0001-8121-8041/work/163294449

Keywords

Keywords

  • Dna, Bioelectric phenomena, Charge exchange, Density functional theory, Ionisation potential, Molecular biophysics, Molecular configurations, Molecular dynamics method, Quantum theory, Solvation