SPECTROSCOPIC EVALUATION OF THE STRUCTURE AND DYNAMICS OF THE HYDROGEN BONDS IN DIFFERENT CRYSTAL MODIFICATION OF POTASSIUM BIIODATE

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1996

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Ohio State University

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The KIO3.HIO3 crystals belong to the family of acidic iodate compounds which is well-known for its ferroelectric phase transitions and has four crystal modifications. Here we report the results of IR and Raman study of vibrational spectra (4000−60cm−1) of α and σ-modifications in the temperature range from 300 to 13 K. The αKIO3 HIO3 crystal (P21/b space group, z=4 at room temperature) is built of two nonequivalent sets of dimers IO3HO3I, joined by strong symmetric hydrogen bond (O...O distance is about 2.5 \AA). At 223 K (Te) the ferroelectric phase transition occurs in this crystal. The stable σ-modification (space group Fdd2,z=24 at room temperature) is formed from structure units of three distinct types:I2O5(OH), which are joined by the H-bound network. In order to understand the normal modes of vibrations in αKIO3HIO3.and σKIO3HIO3, we have carried out lattice dynamics calculations using a generalized valence force field for the dimers [H(IO3)2] and othe structure units. The introduction of the translation and libration coordinates related to the normal coordinate analysis leads to a precise assignment of the frequencies and shows that both stretching and bending vibrations of IO3 groups are strongly coupled with the translational vibrations of the hydrogen atom in case of σ-modification. In the case of σ-modification those vibrations are localized on separate I-O bonds. A comparative analysis of the vibrational spectra and structure is presented. On the base of analysis of vibrational spectra and according to measurementsa of pressure dependencies of the 127I NQR spectra at 77 K it was concluded that the mechanism of ferroelectric phase transition in α-modification of potassium biiodate crystal involves the proton ordering in the double-well potential at Tc.

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aA. I.Barabash, J. Mol. Struct., 270, 517 (1992)


Author Institution: National Academy of Sciences of Ukraine, Institute of Physics; Polish Academy of Sciences, Institute of Low Temperature and Structure Research

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