Effect of ionic solutes on the hydrogen bond network dynamics of water: power spectral analysis of aqueous NaCl solutions

Abstract

To understand the modifications of the hydrogen bond network of water by ionic solutes, power spectra as well as static distributions of the potential energies of tagged solvent molecules and solute ions have been computed from molecular dynamics simulations of aqueous NaCl solutions. The key power spectral features of interest are the presence of high-frequency peaks due to localized vibrational modes, the existence of a multiple time scale or 1/ƒ α frequency regime characteristic of networked liquids, and the frequency of crossover from 1/ƒ α type behavior to white noise. Hydrophilic solutes, such as the sodium cation and the chloride anion, are shown to mirror the multiple time scale behavior of the hydrogen bond network fluctuations, unlike hydrophobic solutes which display essentially white noise spectra. While the power spectra associated with tagged H₂O molecules are not very sensitive to concentration in the intermediate frequency 1/ƒ α a regime, the crossover to white noise is shifted to lower frequencies on going from pure solvent to aqueous alkali halide solutions. This suggests that new and relatively slow time scales enter the picture, possibly associated with processes such as migration of water molecules from the hydration shell to the bulk or conversion of contact ion pairs into solvent-separated ion pairs which translate into variations in equilibrium transport properties of salt solutions with concentration. For anions, cations, and solvent molecules, the trends in the a exponents of the multiple time scale region and the self-diffusivities are found to be strongly correlated.