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Theoretical modeling of the OH stretch infrared spectrum of carboxylic acid dimers based on first-principles anharmonic couplings

J. Chem. Phys. 118, 1735 (2003); doi:10.1063/1.1530573

Issue Date: 22 January 2003

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Gina M. Florio and Timothy S. Zwier
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393

Evgeniy M. Myshakin and Kenneth D. Jordan
Department of Chemistry and Center for Molecular and Materials Simulations, University of Pittsburgh, Pittsburgh, Pennsylvania 15260

Edwin L. Sibert III
Theoretical Chemistry Institute, Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706-1396
Carboxylic acid dimers serve as prototypical systems for modeling the unusual spectral behavior of the hydride stretch fundamental. Large anharmonic effects associated with the pair of cooperatively strengthened OH[centered ellipsis]O[Double Bond]C hydrogen bonds produces complicated infrared spectra in which the OH stretch oscillator strength is spread over hundreds of wave numbers, resulting in a complicated band sub-structure. In this work cubic anharmonic constants are computed along internal coordinates associated with the intramolecular OH stretch, intermolecular stretch, and OH bend internal coordinates for the formic acid and benzoic acid dimers. These are then projected onto the normal coordinates to produce mixed states that are used in computing the OH stretch infrared spectrum. For the benzoic acid dimer the calculations accurately reproduce for three deuterated isotopomers the overall breadth and much of the vibrational sub-structure in the observed spectra. For the formic acid dimer, the spectrum is calculated using a model employing a subset of the cubic force constants as well as using the full cubic force field. The spectra calculated for the formic acid dimer are sparser and somewhat more sensitive to the exact positions of the anharmonically coupled states than that of the benzoic acid dimer. Again semiquantitative agreement with experiment is obtained. ©2003 American Institute of Physics.
History: Received 20 September 2002; accepted 28 October 2002
Permalink: http://link.aip.org/link/?JCPSA6/118/1735/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Ea
    Infrared molecular spectra
  • 33.20.Tp
    Vibrational analysis (molecular spectra)
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • 33.70.Ca
    Molecular oscillator and band strengths, lifetimes, transition moments, and Franck–Condon factors
  • 34.30.+h
    Intramolecular energy transfer; intramolecular dynamics; dynamics of van der Waals molecules
  • 34.20.Gj
    Intermolecular and atom–molecule potentials and forces
  • YEAR: 2003

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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