The liquid-vapor equilibria of TIP4P/2005 and BLYPSP-4F water models determined through direct simulations of the liquid-vapor interface
by Hu, Hongyi; Wang, Feng
In this paper, the surface tension and critical properties for the TIP4P/2005 and BLYPSP-4F models are reported. A clear dependence of surface tension on the van derWaals cutoff radius (r(vdw)) is shown when van der Waals interactions are modeled with a simple cutoff scheme. A linear extrapolation formula is proposed that can be used to determine the infinite r(vdw) surface tension through a few simulations with finite r(vdw). A procedure for determining liquid and vapor densities is proposed that does not require fitting to a profile function. Although the critical temperature of water is also found to depend on the choice of r(vdw), the dependence is weaker. We argue that a r(vdw) of 1.75 nm is a good compromise for water simulations when long-range van der Waals correction is not applied. Since the majority of computational programs do not support rigorous treatment of long-range dispersion, the establishment of a minimal acceptable r(vdw) is important for the simulation of a variety of inhomogeneous systems, such as water bubbles, and water in confined environments. The BLYPSP-4F model predicts room temperature surface tension marginally better than TIP4P/2005 but overestimates the critical temperature. This is expected since only liquid configurations were fit during the development of the BLYPSP-4F potential. The potential is expected to underestimate the stability of vapor and thus overestimate the region of stability for the liquid.
- Journal
- Journal of Chemical Physics
- Volume
- 142
- Issue
- 21
- Year
- 2015
- URL
- https://dx.doi.org/10.1063/1.4922166
- ISBN/ISSN
- 1089-7690; 0021-9606
- DOI
- 10.1063/1.4922166