Hydrogen bond thermodynamic properties of water from dielectric constant data

We apply statistical mechanical principles to derive simple expressions relating the hydrogen bond thermodynamic properties to the static dielectric constant of water. The approach followed by us was to develop an expression for the Kirkwood's structure factor (g) of water, taking into account the dipolar correlations between a central molecule and H-bonded neighbors present in infinite number of shells surrounding the central molecule. The number of H-bonded neighbors in a specific shell was related to the probability P for the various donor/acceptor sites of any given water molecule to be associated. Neglecting cooperativity effects, we evaluated P by focusing only on the correct counting of Ii-bonds formed between various association sites rather than on the oligomer distribution. The theory yielded an extremely simple expression for the structure factor (g) of the fluid at any given temperature in terms of the enthalpy (H) and entropy (S) changes associated with bond formation. The proposed theory was then combined with the Kirkwood-Frohlich theory for evaluating the dielectric constant (Eg) We have demonstrated that the theory correctly predicts the dielectric constant of ice-I without the use of any adjustable parameters. We have then deduced estimates for H-bund thermodynamic properties (H = -5.58 kcal/mole of H-bonds; S = -8.89cal/deg.mole of H-bonds) by fitting the theoretical results for Eo of liquid water to available experimental data over temperatures ranging from 0 degreesC to the critical point of water. The error in the theoretical values was found to be within 1 % of the corresponding experimental values over the entire range of temperatures studied. To further test the theory, we have demonstrated that the temperature variation of the average number of H-bonds per water molecule, calculated using the proposed theory with the above mentioned values for H and S, compares quite well with those estimated from various available spectroscopic and molecular simulation studies. (C) 2000 American Institute of Physics. [S0021-9606(00)50145-7].