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The influence of large-amplitude librational motion on the hydrogen bond energy for alcohol-water complexes

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Author

  • J. Andersen
  • Jimmy Heimdal
  • R. Wugt Larsen

Summary, in English

The far-infrared absorption spectra have been recorded for hydrogen-bonded complexes of water with methanol and t-butanol embedded in cryogenic neon matrices at 2.8 K. The partial isotopic substitution of individual subunits enabled by a dual inlet deposition procedure provides for the first time unambiguous assignments of the intermolecular high-frequency out-of-plane and low-frequency in-plane donor OH librational modes for mixed alcohol-water complexes. The vibrational assignments confirm directly that water acts as the hydrogen bond donor in the most stable mixed complexes and the tertiary alcohol is a superior hydrogen bond acceptor. The class of large-amplitude donor OH librational motion is shown to account for up to 5.1 kJ mol(-1) of the destabilizing change of vibrational zero-point energy upon intermolecular OH center dot center dot center dot O hydrogen bond formation. The experimental findings are supported by complementary electronic structure calculations at the CCSD(T)-F12/aug-cc-pVTZ level of theory.

Department/s

Publishing year

2015

Language

English

Pages

23761-23769

Publication/Series

Physical Chemistry Chemical Physics

Volume

17

Issue

37

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Physical Chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 1463-9084