The Many-Body Expansion for Aqueous Systems Revisited: II. Alkali Metal and Halide Ion-Water Interactions.

We present a detailed study of the many-body expansion (MBE) for alkali metal and halide ion-water interactions and quantify the effect of these ions on the strength of the surrounding aqueous hydrogen bonding environment. Building on our previous work on neutral water clusters [J. P. Heindel and S. S. Xantheas, J. Chem. Theor. Comput. 16 (11), 6843-6855 (2020)], we carry out the MBE for the alkali metal and halide ion-water clusters, Z+/-(H2O)9, where Z = Li+, Na+, K+, Rb+, Cs+, F-, Cl-, Br-, and I- and compare them with the results for a pure water cluster with the same number of "bodies", viz., (H2O)10. The 2-B ion-water (I-W) interaction accounts for a larger percentage of the total cluster binding energy compared to a pure water cluster of the same size, with the total 3-B term being smaller and of opposite sign (repulsive), whereas higher order terms are essentially negligible. The same oscillating behavior around zero for the MBE terms higher than the 5-B with a basis set that was reported for water clusters is also observed for the ion-water clusters considered here, with the basis set superposition error (BSSE) corrections amending this as in the water cluster case. A remarkable, linear anticorrelation between the total 2-B (I-W), the total 2-B (W-W), and also the 3-B (W-W-W) interactions is found, quantifying the effect of the different ions in disrupting and altering (weakening) the neighboring hydrogen bonded water network: stronger (I-W) interactions result in weaker (W-W) interactions. Additional linear correlations across the two series of alkali metals and halide ions were found between the 3-B (I-W-W) and the 2-B (I-W) as well as between the 3-B (I-W-W) and the 3-B (W-W-W) interactions, suggesting the existence of previously unrealized underlying physics governing these 2-B intermolecular and 3-B collective interactions. Our results further suggest a universal behavior of the two different families of ions (alkali metals and halides) for both the correlations of the various components of the total binding energies and the estimate of the 2-B BSSE correction, which is reported to follow a common profile for ion-water and water-water interactions when cast in terms of reduced distances and energies of the respective dimers. We expect the current results that quantify the interplay between ion-water and water-water interactions in aqueous clusters to impact the development of classical, ab initio-based force fields for monatomic ion solvation, whereas the insights into the nature of the BSSE to be critical in future ab initio-based, many-body molecular dynamics studies.