Optimization of crystal nucleation close to a metastable fluid-fluid phase transition

Abstract

The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experimentsThis work has been supported by the MINECO of the Spanish government through Grants No. FIS2012-31025 and FIS2011-22603. LX thanks the financial support from MOST 973 of China (Grants No. 2015CB856800 and 2012CB921404) and National Science Foundation of China (Grants No. 11174006 and 11290162). HES thanks the NSF Chemistry Division for support (grants CHE 0911389, CHE 0908218, and CHE 1213217). SVB thanks the Office of the Academic Affairs of Yeshiva University for funding the Yeshiva University high-performance computer cluster and acknowledges the partial support of this research through Dr. Bernard W. Gamson computational Science Center at Yeshiva College. (FIS2012-31025 - MINECO of the Spanish government; FIS2011-22603 - MINECO of the Spanish government; 2015CB856800 - MOST 973 of China; 2012CB921404 - MOST 973 of China; 11174006 - National Science Foundation of China; 11290162 - National Science Foundation of China; CHE 0911389 - NSF Chemistry Division; CHE 0908218 - NSF Chemistry Division; CHE 1213217 - NSF Chemistry Division; Office of the Academic Affairs of Yeshiva University; Dr. Bernard W. Gamson computational Science Center at Yeshiva College)Published versio