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

doi: 10.1039/c1cp20182d
pmid: 21491035
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.
- University of Göttingen Germany
- Institut für Physikalische Chemie Germany
- Institut für Physikalische Chemie Germany
Ethanol, Methanol, Water, Hydrogen Bonding, Spectrum Analysis, Raman, Spectroscopy, Fourier Transform Infrared, Quantum Theory, Thermodynamics, Raman spectroscopy; FTIR spectroscopy; hydrogen bonding; methanol; ethanol, mesh: mesh:Quantum Theory, mesh: mesh:Hydrogen Bonding, mesh: mesh:Thermodynamics, mesh: mesh:Water, mesh: mesh:Spectroscopy, Fourier Transform Infrared, mesh: mesh:Methanol, mesh: mesh:Ethanol, mesh: mesh:Spectrum Analysis, Raman
Ethanol, Methanol, Water, Hydrogen Bonding, Spectrum Analysis, Raman, Spectroscopy, Fourier Transform Infrared, Quantum Theory, Thermodynamics, Raman spectroscopy; FTIR spectroscopy; hydrogen bonding; methanol; ethanol, mesh: mesh:Quantum Theory, mesh: mesh:Hydrogen Bonding, mesh: mesh:Thermodynamics, mesh: mesh:Water, mesh: mesh:Spectroscopy, Fourier Transform Infrared, mesh: mesh:Methanol, mesh: mesh:Ethanol, mesh: mesh:Spectrum Analysis, Raman
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