TY - JOUR
T1 - Structure and Vibrational Spectrum ofβ-Cs3(HSO4)2[H2-x(P 1-x, Sx)O4] (x~0.5), a New Superprotonic Conductor, and a Comparison withα-Cs3(HSO4)2(H2PO 4)
AU - Haile, Sossina M.
AU - Calkins, Pamela M.
AU - Boysen, Dane
N1 - Funding Information:
This work was supported in part by the National Science Foundation through a National Young Investigator Award, by Battelle National Laboratories, and by the Electric Power Research Institute. The authors thank Scott Kuehner of the University of Washington for assistance with the electron microprobe analyses, and Dr. Wim Klooster of Brookhaven National Laboratories for providing the results of a preliminary refinement of neutron diffraction data. Alex Katz of the California Institute of Technology kindly collected IR and Raman spectra.
Copyright:
Copyright 2004 Elsevier Science B.V., Amsterdam. All rights reserved.
PY - 1998/9
Y1 - 1998/9
N2 - The structure of the new protonic conductor,β-Cs3(HSO4)2(H 2-x(P1-x, Sx)O4) (with a superprotonic transition at 125°C), has been determined by single-crystal X-ray diffraction methods. Structural features of this and the related compound,α-Cs3(HSO4)2(H 2PO4), have been further examined by Raman and IR spectroscopy. The new compound crystallizes in space groupC2/c, contains four formula units in the unit cell, and has anxvalue (in the stoichiometry) of approximately 0.5. X-ray intensity data, collected at room temperature, yielded lattice parametersa=20.04(1),b=7.854(5),c=8.954(5) Å, andβ=100.11(2)° and a unit cell volume of 1387.5(14) Å3, implying a density of 3.304 g/cm3. Within the asymmetric unit, 10 nonhydrogen atoms and 3 hydrogen sites were located. Refinement of the X-ray data using anisotropic temperature factors for all 10 of the former yielded residualswR(F2)=0.0952 andR(F)=0.0358. The structure contains alternating zig-zig chains of anion tetrahedra and cesium ions, in a manner similar to that found inα-Cs3(HSO4)2(H2PO 4) and in CsHSO4-II. The structure is unique, however, in that P and S occupy the same crystallographic position, and there is, accordingly, a variable H content and a partially occupied hydrogen bond. Broader peaks in the Raman spectrum ofβ-Cs3(HSO4)2(H2-x(P 1-xSx)O4) support the assumption of greater structural disorder in this compound than inα-Cs3(HSO4)2(H2PO 4).
AB - The structure of the new protonic conductor,β-Cs3(HSO4)2(H 2-x(P1-x, Sx)O4) (with a superprotonic transition at 125°C), has been determined by single-crystal X-ray diffraction methods. Structural features of this and the related compound,α-Cs3(HSO4)2(H 2PO4), have been further examined by Raman and IR spectroscopy. The new compound crystallizes in space groupC2/c, contains four formula units in the unit cell, and has anxvalue (in the stoichiometry) of approximately 0.5. X-ray intensity data, collected at room temperature, yielded lattice parametersa=20.04(1),b=7.854(5),c=8.954(5) Å, andβ=100.11(2)° and a unit cell volume of 1387.5(14) Å3, implying a density of 3.304 g/cm3. Within the asymmetric unit, 10 nonhydrogen atoms and 3 hydrogen sites were located. Refinement of the X-ray data using anisotropic temperature factors for all 10 of the former yielded residualswR(F2)=0.0952 andR(F)=0.0358. The structure contains alternating zig-zig chains of anion tetrahedra and cesium ions, in a manner similar to that found inα-Cs3(HSO4)2(H2PO 4) and in CsHSO4-II. The structure is unique, however, in that P and S occupy the same crystallographic position, and there is, accordingly, a variable H content and a partially occupied hydrogen bond. Broader peaks in the Raman spectrum ofβ-Cs3(HSO4)2(H2-x(P 1-xSx)O4) support the assumption of greater structural disorder in this compound than inα-Cs3(HSO4)2(H2PO 4).
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U2 - 10.1006/jssc.1998.7861
DO - 10.1006/jssc.1998.7861
M3 - Article
AN - SCOPUS:0000698099
SN - 0022-4596
VL - 139
SP - 373
EP - 387
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
IS - 2
ER -