Testing the adequacy of simple water models at the opposite ends of the phase diagram

The transferability of of few simple rigid non-polarizable water models were tested by Gibbs Ensemble Monte Carlo simulations to predict their vapor-liquid phase equilibria, and by isothermal-isobaric (Parrinello-Rahman) Monte Carlo simulations of the 13 known crystalline phases of ice. The temperature dependence of the corresponding second virial coefficients was also determined and then used to test the internal consistency of the simulated vapor-phase densities. The model predictions appear satisfactory for liquid water for ambient conditions, but they fail to mimic accurately the properties of the ice polymorphs and the orthobaric vapor phase. The major shortcomings of the models were in the overestimation by a factor of two (similar to 4-6 kJ/mol) of the internal energy difference between the high-pressure ice phases and the hexagonal phase. This unacceptable discrepancy is caused by the parameterization to reproduce the density of liquid water at ambient conditions, that accounts for the significant polarization effects in the condensed phases in terms of augmented dipole moments, with the consequent detrimental effect on the estimations of the vapor-phase properties. (c) 2007 Published by Elsevier B.V.