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

Abstract

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.