Woiczikowski P Benjamin, Kubar Tomás, Gutiérrez Rafael, Caetano Rodrigo A, Cuniberti Gianaurelio, Elstner Marcus
Department of Physical and Theoretical Chemistry, Technische Universitat Braunschweig, D-38106 Braunschweig, Germany.
J Chem Phys. 2009 Jun 7;130(21):215104. doi: 10.1063/1.3146905.
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 et al. [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.
我们详细研究了在溶剂存在下具有不同序列和长度的DNA导线的电荷传输特性。我们的方法将大规模量子/经典分子动力学(MD)模拟与基于朗道尔理论的输运计算相结合。沿着MD轨迹计算导线的量子力学传输函数,从而编码了由环境(水、主链、抗衡离子)和内部碱基动力学引起的动态无序的影响。我们表明,碱基对动力学的相关涨落在确定导线的传输特性方面至关重要,并且对于具有低静态无序和高静态无序(碱基电离势的差异)的序列,涨落的影响可能会有很大不同。结果,在所研究的迪克森十二聚体这种具有高静态无序的结构中,由于动态涨落,高传输结构的权重增加,计算得到的平均传输也增加。我们的分析进一步支持了巴顿等人[《美国化学会志》126, 11471 (2004)]提出的电荷转移活性构象的基本直觉。然而,不一定是具有良好堆积接触从而导致大的碱基间跳跃值的DNA构象最重要,而是沿着碱基堆积的电离势平均涨落较小的那些构象。其背后的原因是构象集合导致平均电子耦合,其足够大以实现充分的传输。另一方面,在位能的对齐是控制电荷传输的关键参数。