The physical origin of hydrophobic effects (1601.06889v3)

Abstract: The strength of hydrogen bonding in water is stronger than that of van der waals interaction, therefore water may play an important role in the process of hydrophobic effects. When a hydrophobic solute is dissolved into water, an interface appears between the solute and water. To understand the mechanism of hydrophobic effects, it is necessary to study the structure of water and solute/water interface. In this study, based on the structural studies on water and air/water interface, the hydration free energy is derived, and utilized to investigate the physical origin of hydrophobic effects. According to the discussion on hydration free energy, with increasing solute size, it can be divided into the initial and hydrophobic solvation processes, respectively. In the initial solvation process, hydration free energy is dominated by the hydrogen bonding in interfacial water (topmost water layer at the solute/water interface). However, in the hydrophobic solvation process, the hydration free energy is related to hydrogen bondings of both bulk water and interfacial water. Additionally, various dissolved behaviors of solutes can be expected for different solvation processes. From this, hydrophobic effects can be ascribed to the competition between the hydrogen bondings in bulk water and those in interfacial water.