Soft hydrogen bonds to alkenes: the methanol–ethene prototype under experimental and theoretical scrutiny

Soft hydrogen bonds to alkenes: the methanol–ethene prototype under experimental and theoretical scrutiny
Heger, M.; Mata, R. A. & Suhm, M. A. (2015) 
Chemical Science6(7) pp. 3738-3745.​

Authors
Heger, Matthias; Mata, Ricardo A.; Suhm, Martin A.
Issue Date
2015
Type
Journal Article
Journal
Chemical Science 
Organization
Fakultät für Chemie 
Institut für Physikalische Chemie 
ISSN
2041-6539; 2041-6520
eISSN
2041-6539
Language
English
Abstract
An FTIR spectroscopic study of the elusive hydrogen-bonded methanol–ethene complex, the most elementary example for weak intermolecular alcohol hydrogen bonding to a p 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 ( 3 cm 1) and the overtone intensity attenuation (2 102-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.
Publication of Göttingen University
Yes
Sponsor
Funder: German Research Foundation [Su 121/4]
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