Accurate Modeling of Bromide and Iodide Hydration with Data- Driven Many-Body Potentials

A Caruso and XY Zhu and JL Fulton and F Paesani, JOURNAL OF PHYSICAL CHEMISTRY B, 126, 8266-8278 (2022).

DOI: 10.1021/acs.jpcb.2c04698

Ion-water interactions play a central role in determining the properties of aqueous systems in a wide range of environments. However, a quantitative understanding of how the hydration properties of ions evolve from small aqueous clusters to bulk solutions and interfaces remains elusive. Here, we introduce the second generation of data-driven many-body energy (MB-nrg) potential energy functions (PEFs) representing bromide-water and iodide-water interactions. The MB-nrg PEFs use permutationally invariant polynomials to reproduce two-body and three body energies calculated at the coupled cluster level of theory, and implicitly represent all higher-body energies using classical many body polarization. A systematic analysis of the hydration structure of small Br-(H2O)n and I-(H2O)n clusters demonstrates that the MB-nrg PEFs predict interaction energies in quantitative agreement with "gold standard" coupled cluster reference values. Importantly, when used in molecular dynamics simulations carried out in the isothermal-isobaric ensemble for single bromide and iodide ions in liquid water, the MB-nrg PEFs predict extended X-ray absorption fine structure (EXAFS) spectra that accurately reproduce the experimental spectra, which thus allows for characterizing the hydration structure of the two ions with a high level of confidence.

Return to Publications page