The dielectric relaxation of water in glassy aqueous binary mixtures exhibits an Arrhenius behaviour with a nearly universal activation energy. We here demonstrate that its characteristic relaxation time follows a remarkably general functional dependence on the weight fraction of water for a wide range of molecular systems.10

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The Gibbs-ensemble Monte Carlo methods based on the extended single point charge [H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma, J. Phys. Chem. 91, 6269 (1987)] potential-energy surface have been used to study the clustering of vapor phase water under vapor-liquid equilibrium conditions between 300 and 600 K. It is seen that the number of clusters, as well as the cluster size, increase with temperature. This is primarily due to the increase in vapor density that accompanies the temperature increase at equilibrium. In addition, due to entropic effects, the percentage of clusters that have linear (or open) topologies increases with temperature and dominates over the minimum-energy cyclic topologies at the temperatures studied here. These results are insensitive to the number of molecules used in the simulations and the criterion used to define a water cluster.

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Gibbs ensemble Monte Carlo methods based on a force field that combines the simple point charge [Berendsen et al., in Intermolecular Forces, edited by Pullman (Reidel, Dordrecht, 1981), p. 331] and transferable potentials for phase equilibria [Martin and Siepmann, J. Phys. Chem. B 102, 2659 (1998)] models were used to study the equilibrium properties of binary systems consisting of water and n-alkanes with chain lengths from hexane to hexadecane. In addition, systems where extended linear alkane chains (up to 300 carbon units long) were used to represent amorphous polyethylene were simulated in the presence of water using a connectivity altering osmotic Gibbs ensemble. In these simulations the equilibrium between a liquid water phase and a polymer phase into which water was inserted was studied. The predicted solubilities, which were determined between 350 and 550 K, are in good agreement with experiment, where experimental results are available, and the density of water molecules in the hydrocarbons is approximately 63% as high as in saturated water vapor under the same conditions. At the lower temperatures most of the water exists as monomers; increasing the temperature leads to an increase in the density of water in the alkane phase and hence in the fraction of molecules that participate in clusters. Dimers are the most prevalent clusters in all hydrocarbons and at all temperatures studied, and the fraction of clusters of given size decrease with increasing cluster size. A large fraction of trimers, tetramers, and pentamers, which are the cluster sizes for which topologies have been studied, are cyclic at low temperatures, but at higher temperatures linear structures predominate. The same properties are observed for pure water vapor clusters in equilibrium with the liquid phase, showing that the cluster topologies are not significantly affected by the surrounding hydrocarbon.