The study of correlations between hydrogen bonding characteristics in liquid, sub- and supercritical methanol. Molecular dynamics simulations and Raman spectroscopy analysis

Abstract

Molecular dynamics (MD) studies of hydrogen bonding (H-bonding) in liquid, sub- and supercritical methanol have been performed in a wide range of thermodynamic parameters of state, using various potential models and two H-bond criteria. It was shown that there is the universal correlation between the average number of H-bonds per molecule (n(HB)) and the mole fraction of H-bonded molecules (X(HB)) for the studied thermodynamic parameters of state. The same feature was observed for the correlations between fractions of molecules forming one (f1), two (f2), three (f3) H-bonds and X(HB). These correlations served to fit experimental Raman spectra of methanol recorded under sub- and supercritical conditions. The advantage of the approach used here is that f1, f2, f3 values have a clear physical meaning and are dependent on the values of state parameters.