Matrix-isolation FT-IR and DFT theoretical studies of the intramolecular hydrogen bonding in Mannich bases

J. Paja̧k, M. Rospenk, G. Maes, L. Sobczyk

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

FT-IR Ar-matrix isolated spectra were studied for dichloro- (Cl 2-MB) and tetrachloroderivatives (Cl4-MB) of the ortho Mannich base. The spectra were analyzed based on the DFT calculated frequencies and intensities and compared with those recorded in CCl4 solution in the region of the ν(OH) and ν(OD) vibrations. The matrix-isolated spectra are characterized by narrower ν(OH) and ν(OD) bands with much better resolved fine structure than in solution. The fine structure originates from the anharmonic coupling with the low frequency modes as well as from Fermi resonance. The ν(OD) band shapes can be reproduced exclusively by assuming the Fermi resonance with overtones and summation of the frequencies of modes into which the bridge atoms are involved. The frequency isotopic ratio (ISR) is for both compounds 1.33 while the half-width ratios are equal to 1.82 and 1.94, for Cl2-MB and Cl4-MB, respectively.

Original languageEnglish
Pages (from-to)229-238
Number of pages10
JournalChemical Physics
Volume320
Issue number2-3
DOIs
Publication statusPublished - Jan 5 2006
Externally publishedYes

Keywords

  • DFT calculations
  • FT-IR spectroscopy
  • Mannich bases
  • Matrix-isolation

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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