Ion-specific anomalous water diffusion in aqueous electrolytes: A machine-learned many-body force field study with MACE

Abstract

The dynamics of water in electrolyte solutions exhibits a striking, ion-specific anomaly: the diffusion coefficient of water is enhanced relative to the neat liquid in chaotropic CsI solutions, yet suppressed in kosmotropic NaCl solutions. This phenomenon, long challenging for classical force-field-based molecular dynamics, is studied here using classical molecular dynamics simulations with a many-body machine-learned force field trained within the MACE equivariant graph neural network framework. The force field is trained on energies, forces, and stresses computed at the density functional theory level with the revPBE-D3 exchange–correlation functional, which provides a reliable balance between accuracy and computational efficiency for aqueous systems. Simulations of NaCl and CsI aqueous solutions under ambient conditions over a concentration range of 0.89–3.56 mol/kg reproduce the experimentally observed anomalous diffusion and yield a quantitative improvement over previous results obtained with the DeePMD framework, which is trained on the same theory, particularly for NaCl solutions. This improvement is traced to a stronger Na+–water interaction in the first hydration shell and the non-negligible retarding contribution of the second hydration shell of Na+. For CsI solutions, the water acceleration is shown to be primarily driven by the anion I−, whose diffuse and weakly structured hydration shell facilitates rapid water exchange with the bulk. These results are rationalized through a shell-decomposition analysis of time-dependent water diffusivities and ion–oxygen potentials of mean force, providing a coherent microscopic picture of the acceleration–retardation mechanism in the studied aqueous electrolytes.