Issue 1, 2023

Raising the benchmark potential of a simple alcohol-ketone intermolecular balance

Abstract

2-Butanone offers two hydrogen bond docking variants to a solvating methanol which are cleanly separated by supersonic jet infrared absorption spectroscopy in the OH-stretching range, resolving earlier action spectroscopy indeterminacies for this elementary case of an intermolecular alcohol-ketone balance. The solvent preference for the shorter chain side is unambiguously derived from the spectra of homologous compounds. It is analysed in terms of competing steric and dispersion interactions and the resulting energy differences across a low interconversion barrier. Fortuitous cancellations are discussed and quantitative energy deficiencies of the employed DFT approaches are suggested. Some benchmarkable experimental observations: at low temperature, a single methanol molecule prefers the methyl-sided oxygen lone pair of 2-butanone over the ethyl-sided lone pair by 1–2 kJ mol−1, the trans butane backbone is conserved in both low-lying isomers, the OH-stretching fundamentals differ by 47(2) cm−1.

Graphical abstract: Raising the benchmark potential of a simple alcohol-ketone intermolecular balance

Supplementary files

Article information

Article type
Paper
Submitted
02 nov. 2022
Accepted
28 nov. 2022
First published
29 nov. 2022
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 384-391

Raising the benchmark potential of a simple alcohol-ketone intermolecular balance

C. Zimmermann, A. C. Dorst and M. A. Suhm, Phys. Chem. Chem. Phys., 2023, 25, 384 DOI: 10.1039/D2CP05141A

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