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  • Polyphosphides  (1)
  • Wiley-Blackwell  (1)
  • Munksgaard International Publishers
  • 1
    ISSN: 0044-2313
    Keywords: Polyphosphides ; Zintl-phases M3X11 (M = Na, K, Rb, Cs; X = P, As) ; P113-, As113- cage anion ; preparation ; vibrational spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 53. Preparation, Properties, and Vibrational Spectra of the Cage Anions P113- and As113-The Zintl-phases M3X11 (M = Na, K, Rb, Cs; X = P, As) are prepared from the elements or from M3X7 and X. The compounds undergo a first-order phase transition from the crystalline to the plastically crystalline state. Unit cell and space group of both modifications and the transition temperature Tc are determined. The vibrational spectra of the crystalline compounds and the Raman spectrum of the P113- anion in en-solution as well are measured. The assignment of the frequencies is given, based on the 32-D3 symmetry of the X113- cage anion. Normal coordinate analysis is carried out in terms of Cartesian coordinates to avoid the problem of redundancies in using internal coordinates. The force constants [mdyn Å-1] obtained for the characteristic bonds r, s, and t are: fppr = 1.34, fpps = 1.20, fppt = 1.08; fAsAsr = 1.1, fAsAss = 0.91. Normal vibrations and the potential energy distribution (PED) are discussed.
    Notes: Die Zintl-Phasen M3X11 (M = Na, K, Rb, Cs; X = P, As) werden aus den Elementen oder aus M3X7 und X synthetisiert. Die Verbindungen durchlaufen einen Phasenübergang 1. Ordnung vom kristallinen zum plastisch-kristallinen Zustand. Elementarzelle und Raumgruppe beider Modifikationen sowie Übergangstemperaturen Tc wurden bestimmt. Die Schwingungsspektren der kristallinen Verbindungen sowie das Raman-Spektrum des Anions P113- in en-Lösung wurden gemessen. Die Zuordnung der Schwingungsfrequenzen gelingt auf der Basis der Symmetrie 32-D3 der Käfiganionen X113-. Die Normalkoordinatenanalyse erfolgte in kartesischen Koordinaten, wodurch das in inneren Koordinaten auftretende Redundanzproblem vermieden wird. Auf diesem Wege erhaltene Kraftkonstanten [mdyn Å-1] der charakteristischen Bindungen r, s und t sind: fppr = 1, 34, fpps = 1, 20, fppt = 1, 08; fAsAsr = 1, 1, fAsAss = 0, 96, fAsAst = 0, 91. Die Normalschwingungen und die Verteilung der potentiellen Energie (PED) werden diskutiert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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