The study of correlations between hydrogen bonding characteristics in liquid, sub- and supercritical methanol. Molecular dynamics simulations and Raman spectroscopy analysisElectronic supplementary information (ESI) available. See DOI: 10.1039/c3fd00103b

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 ( f 1 ), two ( f 2 ), three ( f 3 ) 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 f 1 , f 2 , f 3 values have a clear physical meaning and are dependent on the values of state parameters.