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 H-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 ...

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