A combined Raman- and infrared jet study of mixed methanol-water and ethanol-water clusters

Phys Chem Chem Phys. 2011 Aug 21;13(31):14050-63. doi: 10.1039/c1cp20182d. Epub 2011 Apr 13.

Abstract

The vibrational dynamics of vacuum-isolated hydrogen-bonded complexes between water and the two simplest alcohols is characterized at low temperatures by Raman and FTIR spectroscopy. Conformational preferences during adaptive aggregation, relative donor/acceptor strengths, weak secondary hydrogen bonding, tunneling processes in acceptor lone pair switching, and thermodynamic anomalies are elucidated. The ground state tunneling splitting of the methanol-water dimer is predicted to be larger than 2.5 cm(-1). Two types of alcohol-water trimers are identified from the spectra. It is shown that methanol and ethanol are better hydrogen bond donors than water, but even more so better hydrogen bond acceptors. As a consequence, hydrogen bond induced red shifts of OH modes behave non-linearly as a function of composition and the resulting cluster excess quantities correspond nicely to bulk excess enthalpies at room temperature. The effects of weak C-H···O hydrogen bonds are quantified in the case of mixed ethanol-water dimers.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Ethanol / chemistry*
  • Hydrogen Bonding
  • Methanol / chemistry*
  • Quantum Theory
  • Spectroscopy, Fourier Transform Infrared
  • Spectrum Analysis, Raman
  • Thermodynamics
  • Water / chemistry*

Substances

  • Water
  • Ethanol
  • Methanol