The benefits of alternation and alkylation: large amplitude hydrogen bond librational modes of alcohol trimers and tetramers

Literature Information

Publication Date 2010-02-16
DOI 10.1039/B925578H
Impact Factor 3.676
Authors

R. Wugt Larsen, M. A. Suhm


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Abstract

Intermolecular hydrogen bond librational modes in cyclic trimers and tetramers of methanol and t-butyl alcohol isolated at low temperature in pulsed supersonic jet expansions are observed by direct absorption spectroscopy in the far-infrared region. The large amplitude librational modes probe the strength and directionality of the intermolecular hydrogen bonds. In addition, their frequency and intensity is very sensitive to the angle which the alkyl groups form with the hydrogen bonded ring. Theoretical predictions which fail to describe the trends in cluster size, alkylation and symmetry splitting reported in this work are likely to miss important ingredients of the underlying intermolecular interaction. Analysis of the vibrational correlation diagram between planar and puckered tetramer structures circumvents some deficiencies of approximate treatments.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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