The Six Isomers of the Cyclohexanol Dimer: A Delicate Test for Dispersion Models.
cyclohexanol
hydrogen bonding
jet spectroscopy
molecular recognition
rotational spectroscopy
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
10 08 2020
10 08 2020
Historique:
received:
07
04
2020
revised:
11
05
2020
pubmed:
13
5
2020
medline:
13
5
2020
entrez:
13
5
2020
Statut:
ppublish
Résumé
The cyclohexanol homodimer acts as a delicate test model of the role of dispersion forces in intermolecular association. Whereas phenol produces a single dimer, the suppression of π interactions and the larger conformational flexibility in cyclohexanol results in multiple isomerism, with six competing dimers of the free molecule being observed in a supersonic jet expansion. Rotational spectroscopy reveals accurate structural data, specifically the formation of homo- and heterochiral diastereoisomers and the presence of both equatorial and axial forms in the dimers. Four dispersion-corrected density-functional molecular orbital calculations were tested against the experiment, with B3LYP-D3(BJ) offering good structural reproducibility with an Alrich's triple-ζ basis set. However, the prediction of the dimer energetics is largely model-dependent, thus offering a testbed for the validation of dispersion-corrected computational models.
Identifiants
pubmed: 32396706
doi: 10.1002/anie.202005063
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
14081-14085Informations de copyright
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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