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

dc.contributor.authorHeger, Matthias
dc.contributor.authorMata, Ricardo A.
dc.contributor.authorSuhm, Martin A.
dc.date.accessioned2015-07-17T08:29:18Z
dc.date.available2015-07-17T08:29:18Z
dc.date.issued2015
dc.relation.ISSN2041-6539
dc.identifier.urihttp://resolver.sub.uni-goettingen.de/purl?gs-1/11976
dc.description.abstractAn 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.
dc.language.isoeng
dc.rightsopenAccess
dc.rights.urihttp://creativecommons.org/licenses/by/3.0/
dc.subjectalkenes; methanol– ethene prototype; FTIR spectroscopic
dc.titleSoft hydrogen bonds to alkenes: the methanol–ethene prototype under experimental and theoretical scrutiny
dc.typejournalArticle
dc.identifier.doi10.1039/C5SC01002K
dc.type.versionpublishedVersion
dc.relation.pISSN2041-6520
dc.bibliographicCitation.volume6
dc.bibliographicCitation.issue7
dc.bibliographicCitation.firstPage3738
dc.bibliographicCitation.lastPage3745
dc.type.subtypejournalArticle
dc.description.statuspeerReviewed
dc.bibliographicCitation.journalChem. Sci.


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