In molecular dynamics (MD) simulation, large-scale density fluctuations bring about difficulties in evaluating the critical point from coexisting vapor-liquid densities. This study proposes a gravity perturbation method that improves the stability of vapor-liquid coexisting phases near the critical point by introducing gravity and boundary walls. Trial simulations were performed with a modified flexible SPC-TR (Toukan-Rahman) model and a critical point obtained for water (TC=377.6°C, ρC=0.302gcm-3) was in good agreement with the experimental data (TC=374.0°C, ρC=0.322gcm-3). The method was also applied to NaCl-water mixtures and it was found that simulations were greatly facilitated with the technique. The gravity perturbation method allows reliable determination of phase behavior in the vicinity of a critical point.
- Critical properties
- Molecular simulation
- Vapor-liquid phase equilibrium
ASJC Scopus subject areas
- Chemical Engineering(all)
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry