Stretching frequency distribution and hydrogen bond thermodynamics in water as calculated from ir spectra using the fluctuation model

Abstract

This paper analyzes recent data on statistical distribution of OH vibration frequencies of liquid water calculated from the IR spectra of HOD molecules. The data are analyzed in terms of the hydrogen bond fluctuation concept. Two temperature invariant functions providing a reconstruction of the whole set of initial data and the statistical integral permitting one to calculate the configuration contributions to the internal energy, entropy, and heat capacity of liquid water over a wide temperature range are found and approximated analytically. The calculated heat capacity is in good agreement with thermophysical experimental data.