Theoretical study of the O-H stretching band in 3-hydroxy-2-methyl-4-pyrone

V. Alexandrov, D. M.A. Smith, H. Rostkowska, M. J. Nowak, L. Adamowicz, W. McCarthy

Research output: Contribution to journalArticlepeer-review

15 Scopus citations


The infrared spectrum of 3-hydroxy-2-methyl-4-pyrone reveals an O-H stretching frequency roughly 200 cm-1 lower than that of a typical alcohol group. The frequency lowering results from intramolecular hydrogen bonding between the alcohol and ketone groups. In this work, the stretching and bending vibrations of the O-H group in 3-hydroxy-2-methyl-4-pyrone are studied with a theoretical methodology more rigorous than the conventional harmonic approximation. A two-dimensional potential energy surface in internal coordinates corresponding to different hydrogen positions in the plane of the molecule is calculated with the use of the second order Møller-Plesset perturbation theory. To include all possible variations in kinetic energy in a large amplitude vibrational mode, g-matrix elements with variable values are employed. The analytical expression for the Hamiltonian matrix elements of the two-dimensional vibrational problem in a basis of shifted Gaussian functions is derived. Expectation values for the O-H stretch nuclear states are variationally determined with the use of shifted Gaussian functions as the basis set. The results of the calculations are compared with the recent matrix-isolation infrared (IR) spectroscopic results. The calculated transition frequency corresponding to the in-plane O-H stretching is found to be in good agreement with the experimental value.

Original languageEnglish (US)
Pages (from-to)9685-9693
Number of pages9
JournalJournal of Chemical Physics
Issue number23
StatePublished - Jun 15 1998

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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