Fluctuation theory of hydrogen bonding applied to vibration spectra of HOD molecules in liquid water. I. Raman spectra

Abstract

Statistical distributions of the frequencies of OH vibrations calculated from the experimental Raman spectra of HOD molecules over the temperature range of 10–200 C using the recently developed deconvolution technique have been analysed in the framework of fluctuation theory of hydrogen bonding. Two temperature independent functions that are the basis of the Zhukovsky theory for describing the temperature transformation of frequency distribution functions of OH vibrations in a statistical ensemble of O—H…O bonds were established and analytically approximated. This made it possible to reconstruct the entire set of initial spectra and to extrapolate their forms to a wider temperature range. These results support the continuum model of liquid water structure.