Dynamics of hydrogen bond exchange in carboxylic acid dimers
- 15 September 1981
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 75 (6) , 2914-2918
- https://doi.org/10.1063/1.442380
Abstract
The simultaneous hydrogen bond exchange within carboxylic acid dimers is investigated by ab initio quantum chemical calculations and by computations of nuclear dynamics. A significant lowering of the potential barrier to ∼60 kJ/mol has been achieved by extensive structure optimization. The calculations suggest that the proton motion is coupled to a deformation motion of the frame of heavy nuclei. The flexible model treatment of this cooperative nuclear motion yields low vibrational and tunneling frequencies.Keywords
This publication has 23 references indexed in Scilit:
- Dynamics of proton tautomerism in 2,5-dihydroxy-p-benzoquinone: A 13C NMR and CNDO studyChemical Physics Letters, 1979
- Synthesis and reactions of the highly mutagenic 7,8-diol 9,10-epoxides of the carcinogen benzo[a]pyreneJournal of the American Chemical Society, 1977
- Molecular orbital studies of hydrogen bondsTheoretical Chemistry Accounts, 1977
- Intramolecular hydrogen bond. Ab initio MO calculations on the enol tautomer of malondialdehydeJournal of the American Chemical Society, 1975
- Far-infrared relaxation in the isolated formic acid dimer molecule: Possibility of fast proton tunneling in a hydrogen bondThe Journal of Chemical Physics, 1974
- OH overtone bands and potential energy curves of the hydrogen-bonded formic and acetic acidsJournal of Molecular Spectroscopy, 1972
- Non-empirical calculations on the intramolecular rearrangement in the dimer of formic acidChemical Physics Letters, 1971
- A Reinvestigation of the Structure of Monomer and Dimer Formic Acid by Gas Electron Diffraction Technique.Acta Chemica Scandinavica, 1969
- Microwave Rotation Spectra of Hydrogen-Bonded MoleculesThe Journal of Chemical Physics, 1964
- An Electron Diffraction Investigation of the Monomers and Dimers of Formic, Acetic and Trifluoroacetic Acids and the Dimer of Deuterium Acetate1Journal of the American Chemical Society, 1944