No abstract

The vapor-liquid equilibria of three recently proposed water models have been computed using Gibbs-Duhem simulations. These models are TIP4P/Ew, TIP4P/2005, and TIP4P/ice and can be considered as modified versions of the TIP4P model. By design TIP4P reproduces the vaporization enthalpy of water at room temperature, whereas TIP4P/Ew and TIP4P/2005 match the temperature of maximum density and TIP4P/ice the melting temperature of water. Recently, the melting point for each of these models has been computed, making it possible for the first time to compute the complete vapor-liquid equilibria curve from the triple point to the critical point. From the coexistence results at high temperature, it is possible to estimate the critical properties of these models. None of them is capable of reproducing accurately the critical pressure or the vapor pressures and densities. Additionally, in the cases of TIP4P and TIP4P/ice the critical temperatures are too low and too high, respectively, compared to the experimental value. However, models accounting for the density maximum of water, such as TIP4P/Ew and TIP4P/2005 provide a better estimate of the critical temperature. In particular, TIP4P/2005 provides a critical temperature just 7 K below the experimental result as well as an extraordinarily good description of the liquid densities from the triple point to the critical point. All TIP4P-like models present a ratio of the triple point temperature to the critical point temperature of about 0.39, compared with the experimental value of 0.42. As is the case for any effective potential neglecting many body forces, TIP4P/2005 fails in describing simultaneously the vapor and the liquid phases of water. However, it can be considered as one of the best effective potentials of water for describing condensed phases, both liquid and solid. In fact, it provides a completely coherent view of the phase diagram of water including fluid-solid, solid-solid, and vapor-liquid equilibria.

All available numerical data on virial coefficients along with simulation results for the compressibility factors of hard body fluids and their mixtures have been compiled. Practically all relevant theories for these fluids (lattice theories, specific methods for discontinuous potentials, integral and integro-differential theories, expansion and resummation techniques, as well as perturbation and conformal theories) are reviewed and their results are compared with the data. The individual methods are critically assessed and their advantages and limits are discussed.

We present a new and computationally efficient methodology using osmotic ensemble Monte Carlo (OEMC) simulation to calculate chemical potential-concentration curves and the solubility of aqueous electrolytes. The method avoids calculations for the solid phase, incorporating readily available data from thermochemical tables that are based on well-defined reference states. It performs simulations of the aqueous solution at a fixed number of water molecules, pressure, temperature, and specified overall electrolyte chemical potential. Insertion/deletion of ions to/from the system is implemented using fractional ions, which are coupled to the system via a coupling parameter λ that varies between 0 (no interaction between the fractional ions and the other particles in the system) and 1 (full interaction between the fractional ions and the other particles of the system). Transitions between λ-states are accepted with a probability following from the osmotic ensemble partition function. Biasing weights associated with the λ-states are used in order to efficiently realize transitions between them; these are determined by means of the Wang-Landau method. We also propose a novel scaling procedure for λ, which can be used for both nonpolarizable and polarizable models of aqueous electrolyte systems. The approach is readily extended to involve other solvents, multiple electrolytes, and species complexation reactions. The method is illustrated for NaCl, using SPC/E water and several force field models for NaCl from the literature, and the results are compared with experiment at ambient conditions. Good agreement is obtained for the chemical potential-concentration curve and the solubility prediction is reasonable. Future improvements to the predictions will require improved force field models.

No abstract