Water model for hydrophobic cavities: structure and energy from quantum-chemical calculations

This ab initio study aims to design a series of large water clusters having a hollow clathrate-like cage able to host hydrophobic solutes of various sizes. Starting from the (H2O)n (n = 18, 20, 24 and 28) hollow cages, water layers have been added in a stepwise manner in order to model the configuration of water molecules beyond the primary shell. The large (H2O)100, (H2O)120 and (H2O)140 clusters complete the hydrogen bonding network of the cage with optimal and regular tiling of the do-, tetra-decahedron and hexa-decahedron, respectively. This study is corroborated by an investigation of dense water clusters up to the (H2O)123 one, being highly consistent with experimental data on ice concerning the electronic and zero-point energies for aggregate formation at 0 K and enthalpy and entropy at 273 K. The cavity creation profoundly alters the orientation of water molecules compared with those found in dense clusters. Nevertheless, such a large reorganization is necessary to maximize the water-water attraction by making it similar to the one found in dense clusters. The cage formation is an endothermic process; however, the computed values are large compared with previous reports for hydrocarbon aqueous solutions. Larger clusters are required for a more fruitful comparison.