Are There Immobilized Water Molecules around Hydrophobic Groups? Aqueous Solvation of Methanol from First Principles

Structural, dynamical, bonding, and electronic properties of water molecules around a soluted methanol molecule are studied from first principles. The results are compatible with experiments and qualitatively support the conclusions of recent classical molecular dynamics simulations concerning the controversial issue on the presence of "immobilized" water molecules around hydrophobic groups: the hydrophobic solute slightly reduces the mobility of many surrounding water molecules rather than immobilizing just the few ones which are closest to the methyl group. By generating maximally localized Wannier functions, a detailed description of the polarization effects in both solute and solvent molecules is obtained, which better elucidates the solvation process.