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Title: The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer

Abstract

The effect of strong intermolecular hydrogen bonding on torsional degrees of freedom is investigated by far-infrared absorption spectroscopy for different methanol dimer isotopologues isolated in supersonic jet expansions or embedded in inert neon matrices at low temperatures. For the vacuum-isolated and Ne-embedded methanol dimer, the hydrogen bond OH librational mode of the donor subunit is finally observed at ∼560 cm{sup −1}, blue-shifted by more than 300 cm{sup −1} relative to the OH torsional fundamental of the free methanol monomer. The OH torsional mode of the acceptor embedded in neon is observed at ∼286 cm{sup −1}. The experimental findings are held against harmonic predictions from local coupled-cluster methods with single and double excitations and a perturbative treatment of triple excitations [LCCSD(T)] and anharmonic. VPT2 corrections at canonical MP2 and density functional theory (DFT) levels in order to quantify the contribution of vibrational anharmonicity for this important class of intermolecular hydrogen bond vibrational motion.

Authors:
; ;  [1]; ; ;  [2]
  1. Institut für Physikalische Chemie, Universität Göttingen, Tammannstr. 6, D-37077 Göttingen (Germany)
  2. MAX-IV Laboratory, Lund University, P. O. Box 118, SE-22100 Lund (Sweden)
Publication Date:
OSTI Identifier:
22415318
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 17; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; BONDING; DEGREES OF FREEDOM; DENSITY FUNCTIONAL METHOD; DIMERS; EXCITATION; FORECASTING; HYDROGEN; MATRIX ISOLATION; METHANOL; NEON

Citation Formats

Kollipost, F., Heger, M., Suhm, M. A., Andersen, J., Mahler, D. W., Wugt Larsen, R., E-mail: rewl@kemi.dtu.dk, and Heimdal, J. The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer. United States: N. p., 2014. Web. doi:10.1063/1.4900922.
Kollipost, F., Heger, M., Suhm, M. A., Andersen, J., Mahler, D. W., Wugt Larsen, R., E-mail: rewl@kemi.dtu.dk, & Heimdal, J. The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer. United States. https://doi.org/10.1063/1.4900922
Kollipost, F., Heger, M., Suhm, M. A., Andersen, J., Mahler, D. W., Wugt Larsen, R., E-mail: rewl@kemi.dtu.dk, and Heimdal, J. Fri . "The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer". United States. https://doi.org/10.1063/1.4900922.
@article{osti_22415318,
title = {The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer},
author = {Kollipost, F. and Heger, M. and Suhm, M. A. and Andersen, J. and Mahler, D. W. and Wugt Larsen, R., E-mail: rewl@kemi.dtu.dk and Heimdal, J.},
abstractNote = {The effect of strong intermolecular hydrogen bonding on torsional degrees of freedom is investigated by far-infrared absorption spectroscopy for different methanol dimer isotopologues isolated in supersonic jet expansions or embedded in inert neon matrices at low temperatures. For the vacuum-isolated and Ne-embedded methanol dimer, the hydrogen bond OH librational mode of the donor subunit is finally observed at ∼560 cm{sup −1}, blue-shifted by more than 300 cm{sup −1} relative to the OH torsional fundamental of the free methanol monomer. The OH torsional mode of the acceptor embedded in neon is observed at ∼286 cm{sup −1}. The experimental findings are held against harmonic predictions from local coupled-cluster methods with single and double excitations and a perturbative treatment of triple excitations [LCCSD(T)] and anharmonic. VPT2 corrections at canonical MP2 and density functional theory (DFT) levels in order to quantify the contribution of vibrational anharmonicity for this important class of intermolecular hydrogen bond vibrational motion.},
doi = {10.1063/1.4900922},
url = {https://www.osti.gov/biblio/22415318}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 141,
place = {United States},
year = {2014},
month = {11}
}