The fluctuation hypothesis of hydrogen bonding

To describe the distortion perturbations of the water molecules in solutions the quantum-mechanical method of partial oscillators has been developed. This method allows one to separate in a simple manner two types of influences on vibrations of OH oscillators, viz. the intermolecular perturbations resulting in the different strengths of hydrogen bonds and intramolecular coupling between stretching vibrations. Here the coupling is treated quite strictly, whereas the intermolecular perturbations are introduced phenomenologically. The calculation of the distribution of distortions among molecules in liquid H₂O and D₂O induced by non-equivalency of the two hydrogen bonds of the water molecule has been made on the basis of the method developed, and the parameters of the mean statistical molecule have been found from the experimental spectrum of HOD. The depolarization ratios of vibrations in Raman spectra of the mean statistical molecules H₂O and D₂O have been computed as an illustration of the possibilities of the proposed calculation method. All the estimates show that the stretching oscillators of H₂O and D₂O molecules are significantly coupled in spite of the great distortion of the symmetry of water molecules in the liquid state.