期刊
CHEMICAL SCIENCE
卷 6, 期 7, 页码 3738-3745出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc01002k
关键词
-
资金
- German Research Foundation [Su 121/4]
An FTIR spectroscopic study of the elusive hydrogen-bonded methanol-ethene complex, the most elementary example for weak intermolecular alcohol hydrogen bonding to a pi cloud, is presented. By isolating the complex in a supersonic jet, the rigorous comparability to high-level quantum chemical calculations is ensured. In stark contrast to classical hydrogen bonds, experimental overtone analysis reveals the harmonic oscillator approximation for the OH red shift to be accurate. Harmonic calculations up to explicitly correlated local coupled-cluster level are thus found to agree very well with experiment. The experimental OH values for the red shift (45 cm(-1)), the small change in diagonal anharmonicity (similar to 3 cm(-1)) and the overtone intensity attenuation (2 x 10(2)-fold) together with theoretical predictions for the preferred structural arrangement and the zero-point-corrected dissociation energy (8 kJ mol(-1)) may thus be regarded as definitive reference values for related systems and for more approximate computational methods. In particular, MP2 calculations are shown to fail for this kind of weak intermolecular interaction.
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