The Six Isomers of the Cyclohexanol Dimer: A Delicate Test for Dispersion Models
Fecha
2020Autor
Juanes, Marcos
Usabiaga Gutiérrez, Imanol
León Ona, Iker
Evangelisti, Luca
Lesarri, Alberto
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Angewandte Chemie International Edition 59(33) : 14081-14085 (2020)
Resumen
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.