Crystal-liquid interfacial free energy via thermodynamic integration

Abstract

A novel thermodynamic integration (TI) scheme is presented to compute the crystal-liquid interfacial free energy (${\gamma }_{\mathrm{cl}}$) from molecular dynamics simulation. The scheme is applied to a Lennard-Jones system. By using extremely short-ranged and impenetrable Gaussian flat walls to confine the liquid and crystal phases, we overcome hysteresis problems of previous TI schemes that stem from the translational movement of the crystal-liquid interface. Our technique is applied to compute ${\gamma }_{\mathrm{cl}}$ for the (100), (110) and (111) orientation of the crystalline phase at three temperatures under coexistence conditions. For one case, namely the (100) interface at the temperature $T=1.0$ (in reduced units), we demonstrate that finite-size scaling in the framework of capillary wave theory can be used to estimate ${\gamma }_{\mathrm{cl}}$ in the thermodynamic limit. Thereby, we show that our TI scheme is not associated with the suppression of capillary wave fluctuations.

arXiv comment11 pages, 8 figures

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• The Gibbs free energy of homogeneous nucleation: from atomistic nuclei to the planar limit
• Direct calculation of the planar NaCl-aqueous solution interfacial free energy at the solubility limit
• Computing the Tolman length for solid-liquid interfaces
• Equilibrium Fluid-Crystal Interfacial Free Energy of Bcc-Crystallizing Aqueous Suspensions of Polydisperse Charged Spheres
• Excess free energy of supercooled liquids at disordered walls
• Predictions of the interfacial free energy along the coexistence line from single-state calculations
• Free energy cost of forming an interface between a crystal and its frozen version