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Article

Pinacolone-Alcohol Gas-Phase Solvation Balances as Experimental Dispersion Benchmarks

Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstr. 6, 37077 Göttingen, Germany
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Academic Editor: Ilya G. Shenderovich
Molecules 2020, 25(21), 5095; https://doi.org/10.3390/molecules25215095
Received: 25 September 2020 / Revised: 28 October 2020 / Accepted: 28 October 2020 / Published: 3 November 2020
The influence of distant London dispersion forces on the docking preference of alcohols of different size between the two lone electron pairs of the carbonyl group in pinacolone was explored by infrared spectroscopy of the OH stretching fundamental in supersonic jet expansions of 1:1 solvate complexes. Experimentally, no pronounced tendency of the alcohol to switch from the methyl to the bulkier tert-butyl side with increasing size was found. In all cases, methyl docking dominates by at least a factor of two, whereas DFT-optimized structures suggest a very close balance for the larger alcohols, once corrected by CCSD(T) relative electronic energies. Together with inconsistencies when switching from a C4 to a C5 alcohol, this points at deficiencies of the investigated B3LYP and in particular TPSS functionals even after dispersion correction, which cannot be blamed on zero point energy effects. The search for density functionals which describe the harmonic frequency shift, the structural change and the energy difference between the docking isomers of larger alcohols to unsymmetric ketones in a satisfactory way is open. View Full-Text
Keywords: dispersion; ketone–alcohol complexes; density functional theory; hydrogen bonds; molecular recognition; vibrational spectroscopy; gas phase; benchmark; pinacolone dispersion; ketone–alcohol complexes; density functional theory; hydrogen bonds; molecular recognition; vibrational spectroscopy; gas phase; benchmark; pinacolone
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MDPI and ACS Style

Zimmermann, C.; Fischer, T.L.; Suhm, M.A. Pinacolone-Alcohol Gas-Phase Solvation Balances as Experimental Dispersion Benchmarks. Molecules 2020, 25, 5095. https://doi.org/10.3390/molecules25215095

AMA Style

Zimmermann C, Fischer TL, Suhm MA. Pinacolone-Alcohol Gas-Phase Solvation Balances as Experimental Dispersion Benchmarks. Molecules. 2020; 25(21):5095. https://doi.org/10.3390/molecules25215095

Chicago/Turabian Style

Zimmermann, Charlotte, Taija L. Fischer, and Martin A. Suhm 2020. "Pinacolone-Alcohol Gas-Phase Solvation Balances as Experimental Dispersion Benchmarks" Molecules 25, no. 21: 5095. https://doi.org/10.3390/molecules25215095

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