Computational Method for Determining the Excess Chemical Potential Using Liquid-Vapor Phase Coexistence Simulations.

Abstract

Molecular dynamics simulations are a powerful tool for probing and understanding the theoretical aspects of chemical systems and solutions. Our research introduces a novel method for determining the excess chemical potential of non-ideal solutions by leveraging the equivalence between the chemical potential of the vapor phase and liquid phase. Traditional approaches have relied on bulk simulations and the integration of pair distribution functions (g(r)), which are computationally intensive to obtain accurate results. In contrast, our method utilizes a liquid-gas system, where determining the vapor pressure allows for a quick and accurate calculation of the excess chemical potential relative to a reference system, e.g., pure solvent. This approach significantly reduces computational effort while maintaining high accuracy and precision. We demonstrate the effectiveness of this method using a simplified Lennard-Jones model, although the method is broadly applicable to a wide range of systems, including those with complex interactions, varying concentrations, and different temperatures. The reduced computational demands and versatility of our approach make it a valuable tool for studying non-ideal solutions, including ionic solutions in molecular simulations.