info:eu-repo/semantics/article
Computational investigation of structure, dynamics and nucleation kinetics of a family of modified Stillinger-Weber model fluids in bulk and free-standing thin films
Fecha
2016-01Registro en:
Gianetti, Melisa Mariel; Haji Akbari, Amir; Longinotti, María Paula; Debenedetti, Pablo Gastón; Computational investigation of structure, dynamics and nucleation kinetics of a family of modified Stillinger-Weber model fluids in bulk and free-standing thin films; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 18; 5; 1-2016; 4102-4111
1463-9076
CONICET Digital
CONICET
Autor
Gianetti, Melisa Mariel
Haji Akbari, Amir
Longinotti, María Paula
Debenedetti, Pablo Gastón
Resumen
In recent years, computer simulations have found increasingly widespread use as powerful tools for studying phase transitions in wide variety of systems. In the particular and very important case of aqueous systems, the commonly used force-fields tend to offer quite different predictions with respect to a wide range of thermodynamic and kinetic properties, including the ease of ice nucleation, the propensity to freeze at a vapor-liquid interface, and the existence of a liquid-liquid phase transition. It is thus of fundamental and practical interest to understand how different features of a given water model affect its thermodynamic and kinetic properties. In this work, we use the forward-flux sampling technique to study the crystallization kinetics of a family of modified Stillinger-Weber (SW) potentials with energy (ε) and length (σ) scales taken from the monoatomic water (mW) model, but with different tetrahedrality parameters (λ). By increasing λ from 21 to 24, we observe the nucleation rate increases by 48 orders of magnitude at a supercooling of ζ = T/Tm = 0.845. Using classical nucleation theory, we are able to demonstrate that this change can largely be accounted for by the increase in Δμ, the thermodynamic driving force. We also perform rate calculations in freestanding thin films of the supercooled liquid, and observe a crossover from surface-enhanced crystallization at λ = 21 to bulk-dominated crystallization for λ ≥ 22.