Understanding the Anomalous Diffusion of Water in Aqueous Electrolytes Using Machine Learned Potentials

The diffusivity of water in aqueous cesium iodide solutions
is
larger than that in neat liquid water and vice versa for sodium chloride
solutions. Such peculiar ion-specific behavior, called anomalous diffusion,
is not reproduced in typical force field based molecular dynamics
(MD) simulations due to inadequate treatment of ion–water interactions.
Herein, this hurdle is tackled by using machine learned atomic potentials
(MLPs) trained on data from density functional theory calculations.
MLP based atomistic MD simulations of aqueous salt solutions reproduce
experimentally determined thermodynamic, structural, dynamical, and
transport properties, including their varied trends in water diffusivities
across salt concentration. This enables an examination of their intermolecular
structure to unravel the microscopic underpinnings of the differences
in their transport properties. While both ions in CsI solutions contribute
to the faster diffusion of water molecules, the competition between
the heavy retardation by Na ions and the slight acceleration by Cl
ions in NaCl solutions reduces their water diffusivity.