Structure and vibrational spectrum of {beta}-Cs{sub 3}(HSO{sub 4}){sub 2}[H{sub 2{minus}x}(P{sub 1{minus}x}, S{sub x})O{sub 4}](x{approximately}0.5), a new superprotonic conductor, and a comparison with {alpha}-Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2}PO{sub 4})
- California Inst. of Tech., Pasadena, CA (United States)
- Univ. of Washington, Seattle, WA (United States)
The structure of the new protonic conductor, {beta}-Cs{sub 3}(HSO{sub 4}){sub 2} (H{sub 2{minus}x} (P{sub 1{minus}x},S{sub x})O{sub 4}) (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, {alpha}-Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2}PO{sub 4}), have been further examined by Raman and IR spectroscopy. The new compound crystallizes in space group C2/c, contains four formula units in the unit cell, and has an x value (in the stoichiometry) of approximately 0.5 X-ray intensity data, collected at room temperature, yielded lattice parameters a = 20.04(1), b = 7.854(5), c = 8.954(5) {angstrom}, and {beta} = 100.11(2){degree} and a unit cell volume of 1387.5(14) {angstrom}{sup 3}, implying a density of 3.304 g/cm{sup 3}. Within the asymmetric unit, 0 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 residuals wR(F{sup 2}) = 0.0952 and R(F) = 0.0358. The structure contains alternating zig-zig chains of anion tetrahedra and cesium ions, in a manner similar to that found in {alpha}-Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2}PO{sub 4}) and in CsHSO{sub 4}-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 of {beta}-Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2{minus}x}(P{sub 1{minus}x}S{sub x})O{sub 4}) support the assumption of greater structural disorder in this compound than in {alpha}-Cs{sub 3}(HSO{sub 4}){sub 2}(H{sub 2}PO{sub 4}).
- Sponsoring Organization:
- National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States); Electric Power Research Inst., Palo Alto, CA (United States)
- OSTI ID:
- 669778
- Journal Information:
- Journal of Solid State Chemistry, Vol. 139, Issue 2; Other Information: PBD: Sep 1998
- Country of Publication:
- United States
- Language:
- English
Similar Records
Structure of Cs{sub 4}(HSO{sub 4}){sub 3}(H{sub 2}PO{sub 4}) single crystals
Proton-Conducting Composites Based on the Cs{sub 4}(HSO{sub 4}){sub 3}(H{sub 2}PO{sub 4}) Compound