NDLI: IR absorption spectroscopy of polarized states of the [D$_{2}$O...D-OD$_{2}$]$^{+}$ ion in crystalline deuterodioxonium perchlorate

Content Provider	Springer Nature Link
Author	Karelin, A. I. Nikitina, Z. K.
Copyright Year	2006
Abstract	Polymorphism of crystalline DClO$_{4}$·2D$_{2}$O 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 v$_{s,as}$(D$_{3}$O) vibrations of the deuterodioxonium group and a rather narrow strong band at 2506 cm$^{−1}$ due to the v$_{as}$(D$_{2}$O) vibrations of the neutral molecular group. The continuous band v$_{as}$(O...D...O) typical of the intracationic hydrogen bond in D$_{5}$O 2 + ClO 4 − is absent in this case. These features point to considerable polarization of the deuterooxonium cation [D$_{2}$O...D-OD$_{2}$]$^{+}$. 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 D$_{2}$O 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 DClO$_{4}$·2D$_{2}$O 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.
Starting Page	1805
Ending Page	1810
Page Count	6
File Format	PDF
ISSN	00360236
Journal	Russian Journal of Inorganic Chemistry
Volume Number	51
Issue Number	11
e-ISSN	15318613
Language	English
Publisher	Nauka/Interperiodica
Publisher Date	2006-01-01
Publisher Place	Moscow
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry Materials Science Inorganic Chemistry

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