Note: Extraction of hydrogen bond thermodynamic properties of water from dielectric constant and relaxation time data

Abstract

We recently proposed a theory [Suresh, J. Chem. Phys. 113, 9727 (2000)]10.1063/1.1320822, based on the principles of statistical mechanics, for describing the temperature variation of static dielectric constant of water and the average number of H-bonds per molecule in the liquid phase. The theoretical model contains three parameters; two of them pertain to the energy and entropy changes accompanying bond-formation, and the third (ε∞) represents the dielectric constant at a frequency that is sufficiently low for atomic and electronic polarization, but sufficiently high for intermolecular relaxation processes involving the movement of permanent dipole moments to be inoperative. In the absence of a consensus in the literature for the value of ε∞ to be used in dielectric constant calculations, it was arbitrarily set to a commonly accepted value of 1.77 (corresponding to refractive index of 1.33). Values for H-bond parameters were then estimated by best fitting model calculations to experimental data for dielectric constant across temperatures ranging from melting to the critical point of water. It is the purpose of the present Note to eliminate the ambiguity on the choice of ε∞ and propose refined values for the H-bond parameters.