The free energy of the metastable supersaturated vapor via restricted ensemble simulations. III. An extension to the Corti and Debenedetti subcell constraint algorithm
C Nie and J Geng and WH Marlow, JOURNAL OF CHEMICAL PHYSICS, 144, 144503 (2016).
In order to improve the sampling of restricted microstates in our previous work C. Nie, J. Geng, and W. H. Marlow, J. Chem. Phys. 127, 154505 (2007); 128, 234310 (2008) and quantitatively predict thermal properties of supersaturated vapors, an extension is made to the Corti and Debenedetti subcell constraint algorithm D. S. Corti and P. Debenedetti, Chem. Eng. Sci. 49, 2717 (1994), which restricts the maximum allowed local density at any point in a simulation box. The maximum allowed local density at a point in a simulation box is defined by the maximum number of particles N-m allowed to appear inside a sphere of radius R, with this point as the center of the sphere. Both N-m and R serve as extra thermodynamic variables for maintaining a certain degree of spatial homogeneity in a supersaturated system. In a restricted canonical ensemble, at a given temperature and an overall density, series of local minima on the Helmholtz free energy surface F(N-m, R) are found subject to different (N-m, R) pairs. The true equilibrium metastable state is identified through the analysis of the formation free energies of Stillinger clusters of various sizes obtained from these restricted states. The simulation results of a supersaturated Lennard-Jones vapor at reduced temperature 0.7 including the vapor pressure isotherm, formation free energies of critical nuclei, and chemical potential differences are presented and analyzed. In addition, with slight modifications, the current algorithm can be applied to computing thermal properties of superheated liquids. Published by AIP Publishing.
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