Simulations of Crystal Nucleation from Solution at Constant Chemical Potential
arXiv:1907.04037
Abstract
A widely spread method of crystal preparation is to precipitate it from a supersaturated solution. In such a process, control of solution concentration is of paramount importance. Nucleation process, polymorph selection, and crystal habits depend crucially on this thermodynamic parameter. When performing simulations in the canonical ensemble as the crystalline phase is deposited the solution is depleted of solutes. This unavoidable modification of the thermodynamic conditions leads to significant artifact. Here we adopt the idea of the constant chemical potential molecular dynamics approach of Perego et al. [J. Chem. Phys. 2015, 142, 144113] to the study of nucleation. Our method allows determining the crystal nucleus size and nucleation rates at constant supersaturation. As an example we study the homogeneous nucleation of sodium chloride from its supersaturated aqueous solution.
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- Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method
- Molecular Dynamics Simulations of Solutions at Constant Chemical Potential
- Homogeneous nucleation of ice
- Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal