Matrix-isolation FTIR studies and theoretical calculations of hydrogen-bonded complexes of imidazole. A comparison between experimental results and different calculation methods

Marlies K. Van Bael, Johan Smets, Kristien Schoone, Linda Houben, William McCarthy, Ludwik Adamowicz, Maciej J. Nowak, Guido Maes

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Abstract

The hydrogen bond interaction between water and imidazole was investigated with the matrix-isolation FTIR spectroscopy coupled to ab initio calculations performed with the RHF and MP2 methods and the parametrized DFT method with the B3LYP hybrid functional. The 6-31G** and 6-31++G** basis sets were used in the calculations. Evaluation of the accuracy of the three methods and the two basis sets was made for noncomplexed imidazole. All three of the methods gave geometries for imidazole in good agreement with the experimental structure. Also, all three levels of theory with both basis sets gave similarly accurate vibrational frequency predictions for monomeric imidazole with a best mean deviation for the DFT/B3LYP/ 6-31++G** method. The assignment of the matrix spectra of the two isomeric H-bond complex species, N-H⋯OH 2 and N⋯H-OH, was performed by comparison with the theoretically predicted IR frequencies and intensities and was further assisted by asymmetrical deuteration experiments. The MP2 and DFT methods employed with the basis set augmented with diffuse functions gave good predictions of the frequency shifts for the vibrational modes directly influenced by the H-bond interaction. For the other vibrational modes, the RHF method performed almost as equally well as the MP2 and DFT methods and we can conclude that this method can provide qualitative and quantitively reliable data on hydrogen-bonded systems.

Original languageEnglish (US)
Pages (from-to)2397-2413
Number of pages17
JournalJournal of Physical Chemistry A
Volume101
Issue number13
StatePublished - Mar 27 1997

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imidazoles
Discrete Fourier transforms
Hydrogen
isolation
hydrogen
matrices
vibration mode
Vibrational spectra
predictions
frequency shift
Hydrogen bonds
interactions
Spectroscopy
hydrogen bonds
deviation
Geometry
imidazole
Water
evaluation
geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Matrix-isolation FTIR studies and theoretical calculations of hydrogen-bonded complexes of imidazole. A comparison between experimental results and different calculation methods. / Van Bael, Marlies K.; Smets, Johan; Schoone, Kristien; Houben, Linda; McCarthy, William; Adamowicz, Ludwik; Nowak, Maciej J.; Maes, Guido.

In: Journal of Physical Chemistry A, Vol. 101, No. 13, 27.03.1997, p. 2397-2413.

Research output: Contribution to journalArticle

Van Bael, Marlies K. ; Smets, Johan ; Schoone, Kristien ; Houben, Linda ; McCarthy, William ; Adamowicz, Ludwik ; Nowak, Maciej J. ; Maes, Guido. / Matrix-isolation FTIR studies and theoretical calculations of hydrogen-bonded complexes of imidazole. A comparison between experimental results and different calculation methods. In: Journal of Physical Chemistry A. 1997 ; Vol. 101, No. 13. pp. 2397-2413.
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