Data-Driven Many-Body Models Enable a Quantitative Description of Chloride Hydration from Clusters to Bulk

We present a new data-driven potential energy function (PEF) describing chloride–water interactions which is developed within the many-body-energy (MB-nrg) theoretical framework. Besides quantitatively reproducing low-order many-body energy contributions, the new MB-nrg PEF is able to correctly predict the interaction energies of small chloride–water clusters calculated at the coupled cluster level of theory. Importantly, classical and quantum molecular dynamics simulations of a single chloride ion in water demonstrate that the new MB-nrg PEF predicts X-ray spectra in close agreement with the experimental results. Comparisons with an popular empirical model and a polarizable PEF emphasize the importance of an accurate representation of short-range many-body effect while demonstrating that pairwise additive representations of chloride–water and water–water interactions are inadequate for correctly representing the hydration structure of chloride in both gas-phase clusters and solution. We believe that the analyses presented in this study provide additional evidence for the accuracy and predictive ability of the MB-nrg PEFs which can then enable more realistic simulations of ionic aqueous systems in different environments.