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IR absorption spectroscopy of polarized states of the [D2O...D-OD2]+ ion in crystalline deuterodioxonium perchlorate

  • Physical Methods of Investigation
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Abstract

Polymorphism of crystalline DClO4·2D2O with 99 at % D has been studied by IR absorption spectroscopy. A new phase has been found, which is easy to identify based on some spectral indications: the spectra show a strong broad band at 2125 cm−1 due to vs,as(D3O) vibrations of the deuterodioxonium group and a rather narrow strong band at 2506 cm−1 due to the vas(D2O) vibrations of the neutral molecular group. The continuous band vas(O...D...O) typical of the intracationic hydrogen bond in D5O +2 ClO −4 is absent in this case. These features point to considerable polarization of the deuterooxonium cation [D2O...D-OD2]+. Its low symmetry is explained by a considerable displacement of the bridging D atom from the center of the strong hydrogen bond to one of the two D2O molecules induced by asymmetric interactions in the crystal field. The ClO −4 ions bound by the hydrogen bonds of dioxonium are also in low-symmetry positions. Upon the crystallization of DClO4·2D2O with ≥10 at % H, a polymorphic isotope effect is observed: the crystal structure depends on H-D isotope dilution, the conditions of thermal treatment of all samples being the same.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    A. I. Karelin & Z. K. Nikitina

Authors
  1. A. I. Karelin
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  2. Z. K. Nikitina
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Original Russian Text © A.I. Karelin, Z.K. Nikitina, 2006, published in Zhurnal Neorganicheskoi Khimii, 2006, Vol. 51, No. 11, pp. 1916–1922.

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Karelin, A.I., Nikitina, Z.K. IR absorption spectroscopy of polarized states of the [D2O...D-OD2]+ ion in crystalline deuterodioxonium perchlorate. Russ. J. Inorg. Chem. 51, 1805–1810 (2006). https://doi.org/10.1134/S0036023606110179

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  • DOI: https://doi.org/10.1134/S0036023606110179

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