A methane-water model for coarse-grained simulations of solutions and clathrate hydrates.

Methane is the prototypic hydrophobic molecule; it has an extremely low solubility in liquid water that leads to phase segregation. On the other hand, at moderate pressures and room temperature, water and methane form hydrate clathrate crystals with a methane to water ratio up to a 1000 times higher than the saturated aqueous phase. This apparent dichotomy points to a subtle balance between the strong water-water hydrogen bonding, responsible for the hydrophobic effect, and water-methane attraction. Capturing these nuances with molecular models requires an appropriate balance of intermolecular interactions. Here we present such a coarse-grained molecular model of water and methane that represents each molecule by a single particle interacting through very short-range interaction potentials. The model is based on the monatomic model of water mW [Molinero, V.; Moore, E. B. J. Phys. Chem. B 2009, 113, 4008] and is between 2 and 3 orders of magnitude more computationally efficient than atomistic models with Ewald sums. The coarse-grained model of this study reproduces the solubility and hydration number of methane in liquid water, the surface tension of the water-methane interface and the equilibrium melting temperature of methane hydrate clathrates with structures sI and sII. To the best of our knowledge this is the first force-field, atomistic or coarse-grained, that reproduces these range of properties of liquid and solid phases of water and methane, making it an efficient and accurate model for the study of the mechanisms of nucleation and growth of clathrates. We expect that the results of this work will also be useful for the modeling of the hydrophobic assembly in aqueous solutions and the development of coarse-grained models of biomolecules with explicit solvation.