Homogeneous nucleation of NaCl in supersaturated solutions

• Published in: Physical chemistry chemical physics : PCCP Vol. 23; no. 47; pp. 26843 - 26852
• Main Authors: Lamas, C, Espinosa, J, Conde, M, Ramírez, J, Montero de Hijes, P, Noya, E, Vega, C, Sanz, E
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 08.12.2021
• Subjects: Approximation; Criteria; Crystallization; Molecular dynamics; Nucleation; Order parameters; Sodium chloride
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d1cp02093e

The seeding method is an approximate approach to investigate nucleation that combines molecular dynamics simulations with classical nucleation theory. Recently, this technique has been successfully implemented in a broad range of nucleation studies. However, its accuracy is subject to the arbitrary choice of the order parameter threshold used to distinguish liquid-like from solid-like molecules. We revisit here the crystallization of NaCl from a supersaturated brine solution and show that consistency between seeding and rigorous methods, like Forward Flux Sampling (from previous work) or spontaneous crystallization (from this work), is achieved by following a mislabelling criterion to select such threshold ( i.e. equaling the fraction of the mislabelled particles in the bulk parent and nucleating phases). This work supports the use of seeding to obtain fast and reasonably accurate nucleation rate estimates and the mislabelling criterion as one giving the relevant cluster size for classical nucleation theory in crystallization studies. Seeding studies of crystal nucleationtuned with the mislabelling criterion are consistentwith methods not reliant on classical nucleation theory.