D. Boda et al., DETERMINATION OF VAPOR-LIQUID-EQUILIBRIUM USING CAVITY-BIASED GRAND-CANONICAL MONTE-CARLO METHOD, Molecular physics, 92(6), 1997, pp. 1067-1072
In a previous paper a new simulation method was introduced for the det
ermination of vapour-liquid equilibrium (VLE) of pure fluids in the gr
and canonical ensemble (Boda, D., Liszi, J., and Szalai, I., 1996, Che
m. Phys. Lett., 256, 474). Its basic idea is the extrapolation of the
pressure in the directions of reciprocal temperature and configuration
al chemical potential via third-order Taylor series expansion: p(beta,
mu). The coefficients of the series can be obtained from fluctuation f
ormulae by performing grand canonical Monte Carlo (GC MC) simulations
on both vapour and liquid sides. It was found that the main shortcomin
g of the method originates from the inaccurate calculation of the pres
sure on liquid side because of the slow convergence of the original GC
MC simulation used. It is now shown that the application of the cavit
y-biased GC MC method of Mezei on the liquid side can overcome this di
fficulty. The linked-cell method to fasten the cavity-searching algori
thm is proposed. The results of test calculations for the Lennard-Jone
s system show excellent agreement with those obtained by the NpT plus
test particle method. The method can be implemented for the determinat
ion of phase separation in mixtures in a straightforward manner.