Finite size effects on liquid-solid phase coexistence and the estimation of crystal nucleation barriers

Abstract

A fluid in equilibrium in a finite volume $V$ with particle number $N$ at a density $\rho =N/V$ exceeding the onset density ${\rho }_f$ of freezing may exhibit phase coexistence between a crystalline nucleus and surrounding fluid. Using a method suitable for the estimation of the chemical potential of dense fluids we obtain the excess free energy due to the surface of the crystalline nucleus. There is neither a need to precisely locate the interface nor to compute the (anisotropic) interfacial tension. As a test case, a soft version of the Asakura-Oosawa model for colloid polymer-mixtures is treated. While our analysis is appropriate for crystal nuclei of arbitrary shape, we find the nucleation barrier to be compatible with a spherical shape, and consistent with classical nucleation theory.

printed in Physical Review Letters,2015

References in corpus (11)

• Accurate determination of crystal structures based on averaged local bond order parameters
• In Search of Colloidal Hard Spheres
• Crystal nucleation of hard spheres using molecular dynamics, umbrella sampling and forward flux sampling: A comparison of simulation techniques
• Influence of polymer excluded volume on the phase behavior of colloid-polymer mixtures
• Curvature Dependence of Surface Free Energy of Liquid Drops and Bubbles: A Simulation Study
• Monte Carlo simulations of the solid-liquid transition in hard spheres and colloid-polymer mixtures
• Crystallization kinetics of colloidal model suspensions: recent achievements and new perspectives
• The equilibrium intrinsic crystal-liquid interface of colloids
• Solvent hydrodynamics speed up crystal nucleation in suspensions of hard spheres
• Crystallization in suspensions of hard spheres: A Monte Carlo and Molecular Dynamics simulation study
• Simulation of fluid-solid coexistence in finite volumes: A method to study the properties of wall-attached crystalline nuclei

Cited by in corpus (21)

• Equilibrium mechanisms of self-limiting assembly
• A classical nucleation theory description of active colloid assembly
• The Young-Laplace equation for a solid-liquid interface
• A perspective on the microscopic pressure (stress) tensor: history, current understanding, and future challenges
• Seeding Approach to nucleation in the NVT ensemble: the case of bubble cavitation in overstretched Lennard Jones fluids
• Interfacial free energy and Tolman length of curved liquid-solid interfaces from equilibrium studies
• Crystallization of hard spheres revisited. II. Thermodynamic modeling, nucleation work, and the surface of tension
• Canonical free-energy barrier of particle and polymer cluster formation
• Do thermodynamically stable rigid solids exist?
• Revealing three-dimensional structure of individual colloidal crystal grain by coherent x-ray diffractive imaging
• How to Quantify and Avoid Finite Size Effects in Computational Studies of Crystal Nucleation: The Case of Heterogeneous Ice Nucleation
• On the determination of phase boundaries via thermodynamic integration across coexistence regions
• Equivalence between condensation and boiling in a Lennard Jones fluid
• Crystallization of hard spheres revisited. I. Extracting kinetics and free energy landscape from forward flux sampling
• Free Energy Barriers for Crystal Nucleation from Fluid Phases
• Shapes of a liquid droplet in a periodic box
• Crystal nuclei in melts: A Monte Carlo simulation of a model for attractive colloids
• How to quantify and avoid finite size effects in computational studies of crystal nucleation: The case of homogeneous crystal nucleation
• Effect of the Composition on the Free Energy of Crystal Nucleation for CuPd Nanoalloys
• Statistical mechanics of crystal nuclei of hard spheres
• The Droplet Formation-Dissolution Transition in Different Ensembles: Finite-Size Scaling from Two Perspectives