Application of continuum field approach to calculation of hydrogen bonding energies in liquid water

Continuum reaction field theory is applied to calculations on liquid water. It is shown that when Onsager's equation is rearranged to a quadratic equation, and a recently found value of the polarizability is employed, its solutions for liquid water yield good agreement with experimental values throughout the whole temperature range. The relatively high value of the heat of vaporization of liquid water is expressed in terms of large dipolar interaction of a water molecule with the environment, which is due to polarization effects. Introduction of repulsive interactions and the use of one adjustable parameter, the free volume, enables prediction of the vapor pressures. The contribution of collective motions to the free energy of inter‐molecular interactions due to hydrogen bonds in liquid water is estimated.