Abstract
Having a good understanding of nucleation is critical for the control of many important processes, such as polymorph selection during crystallization. However, a complete picture of the molecular-level mechanisms of nucleation remains elusive. In this work, we take an in-depth look at the NaCl homogeneous nucleation mechanism through thermodynamics. Distinguished from the classical nucleation theory, we calculate the free energy of nucleation as a function of two nucleus size coordinates: crystalline and amorphous cluster sizes. The free energy surface reveals a thermodynamic preference for a nonclassical mechanism of nucleation through a composite cluster, where the crystalline nucleus is surrounded by an amorphous layer. The thickness of the amorphous layer increases with an increase in supersaturation. The computed free energy landscape agrees well with the composite cluster-free energy model, through which phase specific thermodynamic properties are evaluated. As the supersaturation increases, there is a change in stability of the amorphous phase relative to the solution phase, resulting in a change from one-step to two-step mechanism, seen clearly from the free energy profile along the minimum free energy path crossing the transition curve. By obtaining phase-specific diffusion coefficients, we construct the full mesoscopic model and present a clear roadmap for NaCl nucleation.