Research Article

Identification of hydrogen bond modes in polarized Raman spectra of single crystals of α-oxalic acid dihydrate

  1. Vlasta Mohaček-Grošev1,*,
  2. Jože Grdadolnik2,
  3. Jernej Stare2,
  4. Dušan Hadži2

Article first published online: 27 MAY 2009

DOI: 10.1002/jrs.2308

Issue

Journal of Raman Spectroscopy

Journal of Raman Spectroscopy

Volume 40, Issue 11, pages 1605–1614, November 2009

Additional Information

How to Cite

Mohaček-Grošev, V., Grdadolnik, J., Stare, J. and Hadži, D. (2009), Identification of hydrogen bond modes in polarized Raman spectra of single crystals of α-oxalic acid dihydrate. J. Raman Spectrosc., 40: 1605–1614. doi: 10.1002/jrs.2308

Author Information

  1. 1

    Ruder Bošković Institute, Bijenička c. 54, 10002 Zagreb, Croatia

  2. 2

    National Institute of Chemistry, 1000 Ljubljana, Hajdrihova 19, Slovenia

*Ruder Bošković Institute, Bijenička c. 54, 10002 Zagreb, Croatia.

Publication History

  1. Issue published online: 11 NOV 2009
  2. Article first published online: 27 MAY 2009
  3. Manuscript Accepted: 15 MAR 2009
  4. Manuscript Received: 25 DEC 2008

Funded by

  • Ministry of Science, Technology and Sport of The Republic of Croatia
  • Ministry of Higher Education, Science and Technology of the Republic of Slovenia
Corrected by:

Erratum: Erratum: Identification of hydrogen bond modes in polarized Raman spectra of single crystals of α-oxalic acid dihydrate

Vol. 41, Issue 5, 598, Article first published online: 11 MAY 2010

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Keywords:

  • strong hydrogen bond;
  • oxalic acid dihydrate;
  • Raman spectroscopy;
  • ab initio calculation;
  • CRYSTAL06 program

Abstract

Polarized Raman spectra of single crystals of the α-polymorphs of protonated and deuterated oxalic acid dihydrate were recorded. The interpretation of the spectra is assisted by periodic DFT calculations using the CRYSTAL06 program and by comparison with the infrared spectra of the polycrystalline material. The agreement between the calculated and observed band wavenumbers is fair in the case of low-anharmonicity modes, but marked differences appear for the stretching modes that are strongly anharmonic. A very broad feature, extending between ∼2000 and 1200 cm−1, is attributed to OH stretching. Notable is the topping of this feature by distinct bands that can be attributed to C[DOUBLE BOND]O stretching, H2O scissoring and COH bending coupled to C[BOND]O stretching. The assignments are supported by isotope effects. However, deuteration does not notably affect the wavenumber limits of the broad OH stretching band, which suggests that the potential governing the proton dynamics is of the asymmetric double-minimum type with a very low barrier. The calculated normal coordinates show a strong participation of the bending modes of water molecules in almost all internal acid motions, as well as in the external phonons. Copyright © 2009 John Wiley & Sons, Ltd.

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