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Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics
Article . 2011 . Peer-reviewed
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A combined Raman- and infrared jet study of mixed methanol–water and ethanol–water clusters

Authors: Nedic, Marija; Wassermann, Tobias N.; Larsen, Rene Wugt; Suhm, Martin A.;

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

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.

Country
Germany
Keywords

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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    81
    popularity
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    Top 10%
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    Top 10%
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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
81
Top 10%
Top 10%
Top 10%
Green
hybrid
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