Toward Chemical Accuracy in the Description of Ion-Water Interactions through Many-Body Representations. I. Halide-Water Dimer Potential Energy Surfaces

Despite recent progress, a unified understanding of how ions affect the structure and dynamics of water across different phases remains elusive. Here, we report the development of full-dimensional many-body potential energy functions, called MB-nrg (Many-Body-energy), for molecular simulations of halide ionwater systems from the gas phase to the condensed phase. The MB-nrg potentials are derived entirely from first-principles calculations carried out at the F12 explicitly correlated coupled-cluster level including single, double, and perturbative triple excitations, CCSD(T)-F12, in the complete basis set limit. Building upon the functional form of the MB-pol water potential, the MB-nrg potentials are expressed through the many-body expansion of the total energy in terms of explicit contributions representing one-body, two-body, and three-body interactions, with all higher-order contributions being described by classical induction. The specific focus of this study is on the MB-nrg two-body terms representing the full-dimensional potential energy surfaces (PESs) of the corresponding H2O-X- dimers, with X-= F-, Cl-, Br-, and I-. The accuracy of the MB-nrg PESs is systematically assessed through extensive comparisons with results obtained using both ab initio models and polarizable force fields for energies, structures, and harmonic frequencies of the H2O-X- dimers.