A combined Raman- and infrared jet study of mixed methanol-water and ethanol-water clusters.
作者： Marija Nedić , Tobias N. Wassermann , René Wugt Larsen , Martin A. Suhm
DOI: 10.1039/C1CP20182D
关键词: Acceptor 、 Hydrogen bond 、 Ground state 、 Spectroscopy 、 Lone pair 、 Raman spectroscopy 、 Photochemistry 、 Chemistry 、 Dimer 、 Low-barrier hydrogen bond
摘要: The vibrational dynamics of vacuum-isolated hydrogen-bonded complexes between water and the two simplest alcohols is characterized at low temperatures by Raman FTIR spectroscopy. Conformational preferences during adaptive aggregation, relative donor/acceptor strengths, weak secondary hydrogen bonding, tunneling processes in acceptor lone pair switching, thermodynamic anomalies are elucidated. ground state splitting methanol–water dimer predicted to be larger than 2.5 cm−1. Two types alcohol–water trimers identified from spectra. It shown that methanol ethanol better bond donors water, but even more so acceptors. As a consequence, induced red shifts OH modes behave non-linearly as function composition resulting cluster excess quantities correspond nicely bulk enthalpies room temperature. effects C–H⋯O bonds quantified case mixed ethanol–water dimers.
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