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Title: The mold integration method for the calculation of the crystal-fluid interfacial free energy from simulations

The interfacial free energy between a crystal and a fluid, γ{sub cf}, is a highly relevant parameter in phenomena such as wetting or crystal nucleation and growth. Due to the difficulty of measuring γ{sub cf} experimentally, computer simulations are often used to study the crystal-fluid interface. Here, we present a novel simulation methodology for the calculation of γ{sub cf}. The methodology consists in using a mold composed of potential energy wells to induce the formation of a crystal slab in the fluid at coexistence conditions. This induction is done along a reversible pathway along which the free energy difference between the initial and the final states is obtained by means of thermodynamic integration. The structure of the mold is given by that of the crystal lattice planes, which allows to easily obtain the free energy for different crystal orientations. The method is validated by calculating γ{sub cf} for previously studied systems, namely, the hard spheres and the Lennard-Jones systems. Our results for the latter show that the method is accurate enough to deal with the anisotropy of γ{sub cf} with respect to the crystal orientation. We also calculate γ{sub cf} for a recently proposed continuous version of the hard spheremore » potential and obtain the same γ{sub cf} as for the pure hard sphere system. The method can be implemented both in Monte Carlo and Molecular Dynamics. In fact, we show that it can be easily used in combination with the popular Molecular Dynamics package GROMACS.« less
Authors:
; ;  [1]
  1. Departamento de Química Física, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain)
Publication Date:
OSTI Identifier:
22436623
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 13; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANISOTROPY; COMPUTERIZED SIMULATION; CRYSTAL LATTICES; CRYSTALS; FLUIDS; FREE ENERGY; FUNGI; MOLECULAR DYNAMICS METHOD; MONTE CARLO METHOD; NUCLEATION; POTENTIAL ENERGY