# Multiple Time Scales in Solvation Dynamics of DNA in Aqueous Solution: The Role of Water, Counterions, and Cross-Correlations

Pal, Subrata and Maiti, Prabal K and Bagchi, Biman and Hynes, James T (2006) Multiple Time Scales in Solvation Dynamics of DNA in Aqueous Solution: The Role of Water, Counterions, and Cross-Correlations. In: Journal of Physical Chemistry B, 110 (51). pp. 26396-26402.

 PDF Multiple_Time_Scales_in_Solvation_Dynamics_of_DNA_in_Aqueous_Solution__The_Role_of.pdf Restricted to Registered users only Download (102Kb) | Request a copy

## Abstract

Recent time domain experiments have explored solvation dynamics of a probe located inside a DNA duplex, in an effort to gain information, e.g., on the dynamics of water molecules in the DNA major and minor grooves and their environment. Multiple time constants in the range of a few picoseconds to several nanoseconds were obtained. We have carried out 15 ns long atomistic molecular dynamics simulations to study the solvation dynamics of bases of a 38 base-pair long DNA duplex in an aqueous solution containing counterions. We have computed the energy-energy time correlation function (TCF) of the four individual bases (A, T, G, and C) to characterize the solvation dynamics. All the TCFs display highly nonexponential decay with time. When the trajectories are analyzed with 100 fs time resolution, the TCF of each base shows initial ultrafast decay (with $\tau_1$\approx 60-80 fs) followed by two intermediate components ($\tau_2$\approx 1 ps,$\tau_3$ \approx 20-30 ps), in near complete agreement with a recent time domain experiment on DNA solvation. Interestingly, the solvation dynamics of each of the four different nucleotide bases exhibit rather similar time scales. To explore the existence of slow relaxation at longer times reported recently in a series of experiments, we also analyzed the solvation TCFs calculated with longer time trajectories and with a larger time resolution of 1 ps. In this case, an additional slow component with a time constant of the order of 250 ps is observed. Through an analysis of partial solvation TCFs, we find that the slow decay originates mainly from the interaction of the nucleotides with the dipolar water molecules and the counterions. An interesting negative cross-correlation between water and counterions is observed, which makes an important contribution to relaxation at intermediate to longer times.

Item Type: Journal Article Copyright of this article belongs to American Chemical Society Division of Chemical Sciences > Solid State & Structural Chemistry UnitDivision of Physical & Mathematical Sciences > Physics 06 Mar 2007 19 Sep 2010 04:34 http://eprints.iisc.ernet.in/id/eprint/9584