Osmotic Force Balance Evaluation of Aqueous Electrolyte Osmotic Pressures and Chemical Potentials.

Concentrated aqueous salt solutions are ubiquitous in problems of biological and environmental relevance. The development of accurate force fields that capture the interactions between dissolved species in solution is crucial to simulating these systems to gain molecular insights into the underlying processes under saline conditions. The osmotic pressure is a relatively simple thermodynamic property connecting the experimental and simulation measurements of the associative properties of the ions in solution. Milner [C. Gillespie and S. T. Milner, , 9816 (2020)] proposed a simulation approach to evaluate the osmotic pressures of salts in solution by applying a restraint potential to the ions alone in solution and determining the resulting pressure required to balance that potential, referred to here as the osmotic force balance. Here, we expand Milner's approach, demonstrating that the chemical potentials of the salts in solution as a function of concentration can be fitted to the concentration profiles determined from simulation, additionally providing an analytical expression for the osmotic pressure. This approach is used to determine the osmotic pressures of 15 alkali halide salts in water from simulations. The cross interactions between cations and anions in solution are subsequently optimized to capture their experimental osmotic pressures.