PNNL

Abstract

We report a Many Body Energy (MBE) analysis of aqueous ionic clusters containing anions and cations at the two opposite ends of the Hofmeister series, viz. the kosmotropes Ca2+, SO42- and chaotropes NH4+ and ClO4- with 9 water molecules to quantify the how these ions in altering the interaction between the water molecules in their immediate surrounding. The current results are contrasted to the ones reported earlier for water clusters as well as for alkali metal and halide ion aqueous clusters of the same size, which lie in the middle of the Hofmeister series. Through this analysis, noteworthy differences between the MBE of kosmotropes and chaotropes were identified. The MBE of kosmotropes is dominated by ion-water interactions that extends beyond the 4-body term, the point at which the MBE of pure water converges. The percentage contribution of the 2- B to the total cluster binding energy is noticeably larger. The disruption due to the dominant ion results in weak, unfavorable water-water interactions. The MBE for chaotropes, on the other hand, was found to converge more quickly as it more closely resembles that of pure water clusters. Chaotropes exhibit weaker overall binding energies and ion-water interactions with more favorable water-water interactions, somewhat recovering the pattern of the 2-4 body terms exemplified by pure water clusters. More importantly, both kosmotropic and chaotropic ions exhibit an anticorrelation between the 2-B ion-water (I-W) and water-water (W-W) interactions as well as between the 3-B (I-W-W) and (I-W) interactions. The consideration of two different structural arrangements (ion inside and outside of a water cluster) suggests that fully solvated (ion inside) chaotropes disrupt the hydrogen bonding network in a similar manner as partially solvated (ion outside) kosmotropes and offer useful insights into the modeling requirements of bulk vs. an interface. Finally, the 2-B contribution to the total Basis Set Superposition Error (BSSE) correction for the kosmotropic and chaotropic ions follows the previously reported erf profile vs. intermolecular distance. When scaled for the corresponding dimer energies and distances, a single profile fits the current results together with all previously reported ones for the pure water and halide water clusters.