Geometrical consequences of intermolecular hydrogen bond formation in the formic acid and acetic acid dimers from ab initio MO calculations

Konstantin B. Borisenko, Charles W. Bock, I. Hargittai

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Ab initio molecular orbital calculations on monomer/dimer formic and acetic acids have been performed with the 6-31G* and 6-31G** basis sets, including the electron correlation using second-order Møller-Plesset perturbation theory. Vibrational frequency analyses confirmed the stability of all the computed structures. The computed geometrical changes in dimeric formic and dimeric acetic acids, as compared to their monomers, are in good agreement with the notion of resonance-assisted intermolecular hydrogen bond formation. Trends in the structural changes obtained from electron diffraction were in general confirmed by the calculations, although they failed to predict the difference in the CC bond length observed in the monomeric and dimeric forms of acetic acid. However, the experimental change in the OH bond length upon hydrogen bond formation seems definitely exaggerated. Taking into account our previous results on 2-nitroresorcinol and 2-nitrophenol, this change is now expected to be not larger than 0.02 Å.

Original languageEnglish
Pages (from-to)161-169
Number of pages9
JournalJournal of Molecular Structure: THEOCHEM
Volume332
Issue number1-2
DOIs
Publication statusPublished - Feb 20 1995

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formic acid
Bond length
acetic acid
Acetic Acid
Dimers
Hydrogen
Hydrogen bonds
Formates
Monomers
dimers
Electrons
hydrogen bonds
Electron correlations
Orbital calculations
acids
Vibrational spectra
Molecular orbitals
monomers
Electron diffraction
Acetates

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Condensed Matter Physics

Cite this

Geometrical consequences of intermolecular hydrogen bond formation in the formic acid and acetic acid dimers from ab initio MO calculations. / Borisenko, Konstantin B.; Bock, Charles W.; Hargittai, I.

In: Journal of Molecular Structure: THEOCHEM, Vol. 332, No. 1-2, 20.02.1995, p. 161-169.

Research output: Contribution to journalArticle

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AB - Ab initio molecular orbital calculations on monomer/dimer formic and acetic acids have been performed with the 6-31G* and 6-31G** basis sets, including the electron correlation using second-order Møller-Plesset perturbation theory. Vibrational frequency analyses confirmed the stability of all the computed structures. The computed geometrical changes in dimeric formic and dimeric acetic acids, as compared to their monomers, are in good agreement with the notion of resonance-assisted intermolecular hydrogen bond formation. Trends in the structural changes obtained from electron diffraction were in general confirmed by the calculations, although they failed to predict the difference in the CC bond length observed in the monomeric and dimeric forms of acetic acid. However, the experimental change in the OH bond length upon hydrogen bond formation seems definitely exaggerated. Taking into account our previous results on 2-nitroresorcinol and 2-nitrophenol, this change is now expected to be not larger than 0.02 Å.

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