title: 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 experiments.
authors.affiliation: Departament de Física Fonamental, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.
authors.forename: Jan
authors.initials: J
authors.lastname: Wedekind
authors.affiliation: International Center for Quantum Materials and School of Physics, Peking University, Beijing 100871, China.
authors.forename: Limei
authors.initials: L
authors.lastname: Xu
authors.affiliation: Department of Physics, Yeshiva University, 500 West 185th Street, New York, NY 10033 USA.
authors.forename: Sergey V
authors.initials: SV
authors.lastname: Buldyrev
authors.affiliation: Center for Polymer Studies and Department of Physics, Boston University, Boston, MA 02215 USA.
authors.forename: H Eugene
authors.initials: HE
authors.lastname: Stanley
authors.affiliation: Departament de Física Fonamental, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.
authors.forename: David
authors.initials: D
authors.lastname: Reguera
authors.affiliation: Departament de Física Fonamental, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Franzese