Correlations between ab initio and experimental data for isolated 1: 1 hydrogen-bonded complexes of pyridine and imidazole derivatives with water

J. Smets, W. McCarthy, G. Maes, Ludwik Adamowicz

Research output: Contribution to journalArticle

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Abstract

Correlations between selected ab initio predicted and experimentally observed properties of 1:1 H-bonded complexes of a series of pyridine derivatives with water are investigated. Specifically, relationships are found between the experimentally observed properties of proton affinity, frequency shift, and dipole moments, and the ab initio calculated values of bond distance, interaction energy, frequency shift, IR absorption intensity and charge differences obtained from Mulliken population analysis. The examined correlations were then compared with data collected for pyridine- H2O and imidazole-H2O complexes. Similarities were found between the correlations in the theoretically determined properties and the correlations in experimentally observed parameters. It was also found that well-defined relations could be established between the calculated and observed properties for the pyridine derivatives, but these could not be reliably extended to the imidazole systems. These similarities demonstrate that the presently available ab initio calculations are useful predictors of experimental behavior of H-bonded systems but only for chemically closely related molecules.

Original languageEnglish (US)
Pages (from-to)27-43
Number of pages17
JournalJournal of Molecular Structure
Volume476
Issue number1-3
DOIs
StatePublished - Feb 23 1999

Fingerprint

imidazoles
Hydrogen
pyridines
Derivatives
Water
hydrogen
water
frequency shift
Dipole moment
Protons
affinity
dipole moments
Molecules
Population
protons
pyridine
imidazole
predictions
molecules
interactions

Keywords

  • Correlation
  • Hydrogen-bonded water complexes
  • Imidazole
  • Pyridine derivatives

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Correlations between ab initio and experimental data for isolated 1 : 1 hydrogen-bonded complexes of pyridine and imidazole derivatives with water. / Smets, J.; McCarthy, W.; Maes, G.; Adamowicz, Ludwik.

In: Journal of Molecular Structure, Vol. 476, No. 1-3, 23.02.1999, p. 27-43.

Research output: Contribution to journalArticle

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N2 - Correlations between selected ab initio predicted and experimentally observed properties of 1:1 H-bonded complexes of a series of pyridine derivatives with water are investigated. Specifically, relationships are found between the experimentally observed properties of proton affinity, frequency shift, and dipole moments, and the ab initio calculated values of bond distance, interaction energy, frequency shift, IR absorption intensity and charge differences obtained from Mulliken population analysis. The examined correlations were then compared with data collected for pyridine- H2O and imidazole-H2O complexes. Similarities were found between the correlations in the theoretically determined properties and the correlations in experimentally observed parameters. It was also found that well-defined relations could be established between the calculated and observed properties for the pyridine derivatives, but these could not be reliably extended to the imidazole systems. These similarities demonstrate that the presently available ab initio calculations are useful predictors of experimental behavior of H-bonded systems but only for chemically closely related molecules.

AB - Correlations between selected ab initio predicted and experimentally observed properties of 1:1 H-bonded complexes of a series of pyridine derivatives with water are investigated. Specifically, relationships are found between the experimentally observed properties of proton affinity, frequency shift, and dipole moments, and the ab initio calculated values of bond distance, interaction energy, frequency shift, IR absorption intensity and charge differences obtained from Mulliken population analysis. The examined correlations were then compared with data collected for pyridine- H2O and imidazole-H2O complexes. Similarities were found between the correlations in the theoretically determined properties and the correlations in experimentally observed parameters. It was also found that well-defined relations could be established between the calculated and observed properties for the pyridine derivatives, but these could not be reliably extended to the imidazole systems. These similarities demonstrate that the presently available ab initio calculations are useful predictors of experimental behavior of H-bonded systems but only for chemically closely related molecules.

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