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Article

Dimerization of Acetic Acid in the Gas Phase—NMR Experiments and Quantum-Chemical Calculations

1
Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 166 10 Prague, Czech Republic
2
Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 166 10 Prague, Czech Republic
*
Author to whom correspondence should be addressed.
Academic Editors: Wiktor Zierkiewicz and Steve Scheiner
Molecules 2020, 25(9), 2150; https://doi.org/10.3390/molecules25092150
Received: 31 March 2020 / Revised: 28 April 2020 / Accepted: 30 April 2020 / Published: 4 May 2020
(This article belongs to the Special Issue Spectroscopic Aspects of Noncovalent Interactions)
Due to the nature of the carboxylic group, acetic acid can serve as both a donor and acceptor of a hydrogen bond. Gaseous acetic acid is known to form cyclic dimers with two strong hydrogen bonds. However, trimeric and various oligomeric structures have also been hypothesized to exist in both the gas and liquid phases of acetic acid. In this work, a combination of gas-phase NMR experiments and advanced computational approaches were employed in order to validate the basic dimerization model of gaseous acetic acid. The gas-phase experiments performed in a glass tube revealed interactions of acetic acid with the glass surface. On the other hand, variable-temperature and variable-pressure NMR parameters obtained for acetic acid in a polymer insert provided thermodynamic parameters that were in excellent agreement with the MP2 (the second order Møller–Plesset perturbation theory) and CCSD(T) (coupled cluster with single, double and perturbative triple excitation) calculations based on the basic dimerization model. A slight disparity between the theoretical dimerization model and the experimental data was revealed only at low temperatures. This observation might indicate the presence of other, entropically disfavored, supramolecular structures at low temperatures. View Full-Text
Keywords: NMR spectroscopy; quantum-chemical calculations; phase transitions; carboxylic acids; hydrogen bonding NMR spectroscopy; quantum-chemical calculations; phase transitions; carboxylic acids; hydrogen bonding
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MDPI and ACS Style

Socha, O.; Dračínský, M. Dimerization of Acetic Acid in the Gas Phase—NMR Experiments and Quantum-Chemical Calculations. Molecules 2020, 25, 2150. https://doi.org/10.3390/molecules25092150

AMA Style

Socha O, Dračínský M. Dimerization of Acetic Acid in the Gas Phase—NMR Experiments and Quantum-Chemical Calculations. Molecules. 2020; 25(9):2150. https://doi.org/10.3390/molecules25092150

Chicago/Turabian Style

Socha, Ondřej, and Martin Dračínský. 2020. "Dimerization of Acetic Acid in the Gas Phase—NMR Experiments and Quantum-Chemical Calculations" Molecules 25, no. 9: 2150. https://doi.org/10.3390/molecules25092150

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