Quantum molecular simulations of micro-hydrated halogen anions

Abstract

We report the results of a detailed and accurate investigation focused on structures and energetics of poly-hydrated halides employing first-principles polarizable halide–water potentials to describe the underlying forces. Following a bottom-up data-driven potential approach, we initially looked into the classical behavior of higher-order X⁻(H₂O)_N clusters. We have located several low-lying energies, such as global and local minima, structures for each cluster, with various water molecules (up to N = 8) surrounding the halide anion (X⁻ = F⁻, Cl⁻, Br⁻, I⁻), employing an evolutionary programming method. It is found that the F⁻–water clusters exhibit different structural configurations than the heavier halides, however independently of the halide anion, all clusters show in general a selective growth with the anion preferring to be connected to the outer shell of the water molecule arrangements. In turn, path-integral molecular dynamics simulations are performed to incorporate explicitly nuclear quantum and thermal effects in describing the nature of halide ion microsolvation in such prototypical model systems. Our data reveal that at low finite temperatures, nuclear quantum effects affect certain structural properties, such as weakening hydrogen bonding between the halide anion and water molecules, with minor distortions in the water network beyond the first hydration shell, indicating local structure rearrangements. Such structural characteristics and the promising cluster size trends observed in the single-ion solvation energies motivated us to draw connections of small size cluster data to the limits of continuum bulk values, toward the investigation of the challenging computational modeling of bulk single ion hydration.