Heterogeneous Occupancy and Vibrational Dynamics of Spatially Patterned Water Molecules

We performed first-principles molecular dynamics simulations of relatively dilute aqueous solutions of sulfate and thiosulfate dianions to analyze the structure, dynamics, and vibrational spectral properties of water molecules around the solute, especially the spatially patterned solvent molecules in the first solvation layer and the extended layers. This study also involves the investigation of dynamics of dangling OH groups in these layers and their role in patterning the water molecules around the dianions. Structural evaluation of the systems is carried out by radial distribution functions, number integrals, and spatial distribution functions. The lifetime of dangling OH groups inside the solvation shell is compared more to that of the bulk. By constructing the O-H groups in three ensembles (S1, S2, and S3) around the anion, we show that the frequency distribution of OH modes in the S1 ensemble show red-shifting for both sulfate and thiosulfate. The O-H groups in the S2 ensemble of the sulfate-water system show red-shifting by 10 cm^-1, while in the case of thiosulfate-water, these O-H groups show blue-shifting by 8 cm^-1. The water molecules in S1 and S2 subensembles have slower dynamics compared to those in the bulk (S3). The dynamics of various kinds of hydrogen bonds were characterized by hydrogen bond population correlation functions. The spectral diffusion of solvation shell O-H modes was performed through a frequency-time correlation function. We find a significant amount of orientational retardation of water molecules in the S1 layer and moderate retardation in the S2 layer as compared to that in the bulk, S3 layer. All these findings, the red shift of the OH stretching frequency in S1 and S2 layers, slowing down of the orientational dynamics of OH vectors in S1 and S2 layers, and less diffusivity of water in S1 and S2 layers, show the long-range kosmotropic effect of multivalent sulfate and thiosulfate oxyanions. Due to the long-range effect, heterogeneous occupancy of water molecules is observed, and the water molecules are found to arrange in a patterned manner in the vicinity of anions with varied local density.