Molecular Dynamics Simulations of Solutions at Constant Chemical Potential

TL;DR

This paper introduces the CμMD method, enabling molecular dynamics simulations at constant chemical potential by controlling molecular exchange with a reservoir, thus overcoming finite-size effects in solution studies.

Contribution

The paper presents a novel CμMD method that maintains constant chemical potential in MD simulations, allowing more accurate modeling of solution processes.

Findings

Successfully applied to urea crystallization in water

Enabled study of crystal growth dynamics under constant supersaturation

Extracted growth rates and free-energy barriers

Abstract

Molecular Dynamics studies of chemical processes in solution are of great value in a wide spectrum of applications, which range from nano-technology to pharmaceutical chemistry. However, these calculations are affected by severe finite-size effects, such as the solution being depleted as the chemical process proceeds, which influence the outcome of the simulations. To overcome these limitations, one must allow the system to exchange molecules with a macroscopic reservoir, thus sampling a Grand-Canonical ensemble. Despite the fact that different remedies have been proposed, this still represents a key challenge in molecular simulations. In the present work we propose the Constant Chemical Potential Molecular Dynamics (C$\mu$MD) method, which introduces an external force that controls the environment of the chemical process of interest. This external force, drawing molecules from a finite reservoir, maintains the chemical potential constant in the region where the process takes place. We have applied the C$\mu$MD method to the paradigmatic case of urea crystallization in aqueous solution. As a result, we have been able to study crystal growth dynamics under constant supersaturation conditions, and to extract growth rates and free-energy barriers.