Temperature, pressure, and isotope effects on the structure and properties of liquid water: a lattice approach

We present a lattice model to describe the effect of isotopic replacement, temperature, and pressure changes on the formation of hydrogen bonds in liquid water. The approach builds upon a previously established generalized lattice theory for hydrogen bonded liquids [B. A. Veytsman, J. Phys. Chem. 94, 8499 (1990)], accounts for the binding order of 1/2 in water-water association complexes, and introduces the pressure dependence of the degree of hydrogen bonding (that arises due to differences between the molar volumes of bonded and free water) by considering the number of effective binding sites to be a function of pressure. The predictions are validated using experimental data on the temperature and pressure dependence of the static dielectric constant of liquid water. The model is found to correctly reproduce the experimentally observed decrease of the dielectric constant with increasing temperature without any adjustable parameters and by assuming values for the enthalpy and entropy of hydrogen bond formation as they are determined from the respective experiments. The pressure dependence of the dielectric constant of water is quantitatively predicted up to pressures of 2 kbars and exhibits qualitative agreement at higher pressures. Furthermore, the model suggests a--temperature dependent--decrease of hydrogen bond formation at high pressures. The sensitive dependence of the structure of water on temperature and pressure that is described by the model rationalizes the different solubilization characteristics that have been observed in aqueous systems upon change of temperature and pressure conditions. The simplicity of the presented lattice model might render the approach attractive for designing optimized processing conditions in water-based solutions or the simulation of more complex multicomponent systems.