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, Ludwik Adamowicz, W. McCarthy

Research output: Contribution to journalArticle

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Abstract

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
JournalThe Journal of Chemical Physics
Volume108
Issue number23
StatePublished - Jun 15 1998

Fingerprint

Stretching
alcohols
Alcohols
Infrared radiation
Hamiltonians
Potential energy surfaces
bending vibration
hydrogen
matrices
Ketones
ketones
Kinetic energy
Hydrogen
vibration mode
isolation
Hydrogen bonds
infrared spectra
perturbation theory
kinetic energy
potential energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Alexandrov, V., Smith, D. M. A., Rostkowska, H., Nowak, M. J., Adamowicz, L., & McCarthy, W. (1998). Theoretical study of the O-H stretching band in 3-hydroxy-2-methyl-4-pyrone. The Journal of Chemical Physics, 108(23), 9685-9693.

Theoretical study of the O-H stretching band in 3-hydroxy-2-methyl-4-pyrone. / Alexandrov, V.; Smith, D. M A; Rostkowska, H.; Nowak, M. J.; Adamowicz, Ludwik; McCarthy, W.

In: The Journal of Chemical Physics, Vol. 108, No. 23, 15.06.1998, p. 9685-9693.

Research output: Contribution to journalArticle

Alexandrov, V, Smith, DMA, Rostkowska, H, Nowak, MJ, Adamowicz, L & McCarthy, W 1998, 'Theoretical study of the O-H stretching band in 3-hydroxy-2-methyl-4-pyrone', The Journal of Chemical Physics, vol. 108, no. 23, pp. 9685-9693.
Alexandrov V, Smith DMA, Rostkowska H, Nowak MJ, Adamowicz L, McCarthy W. Theoretical study of the O-H stretching band in 3-hydroxy-2-methyl-4-pyrone. The Journal of Chemical Physics. 1998 Jun 15;108(23):9685-9693.
Alexandrov, V. ; Smith, D. M A ; Rostkowska, H. ; Nowak, M. J. ; Adamowicz, Ludwik ; McCarthy, W. / Theoretical study of the O-H stretching band in 3-hydroxy-2-methyl-4-pyrone. In: The Journal of Chemical Physics. 1998 ; Vol. 108, No. 23. pp. 9685-9693.
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