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Structure and Vibrational Spectrum of β-Cs_3(HSO_4)_2[H_(2−x)(P_(1−x), S_x)O_4] (x∼0.5), a New Superprotonic Conductor, and a Comparison with α-Cs_3(HSO_4)_2(H_2PO_4)

Haile, Sossina M. and Calkins, Pamela M. and Boysen, Dane A. (1998) Structure and Vibrational Spectrum of β-Cs_3(HSO_4)_2[H_(2−x)(P_(1−x), S_x)O_4] (x∼0.5), a New Superprotonic Conductor, and a Comparison with α-Cs_3(HSO_4)_2(H_2PO_4). Journal of Solid State Chemistry, 139 (2). pp. 373-387. ISSN 0022-4596. http://resolver.caltech.edu/CaltechAUTHORS:20131122-151946002

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Abstract

The structure of the new protonic conductor, β-Cs₃(HSO₄)₂(H₂₋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(H₂PO₄), 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)Å, and β=100.11(2)° and a unit cell volume of 1387.5(14)ų, 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 residuals wR(F²)=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 α-Cs₃(HSO₄)2(H2PO₄) 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 of β-Cs₃(HSO₄)₂(H₂₋ₓ(P₁₋ₓSₓ)O₄) support the assumption of greater structural disorder in this compound than in α-Cs₃(HSO₄)₂(H₂PO₄).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1006/jssc.1998.7861DOIArticle
http://www.sciencedirect.com/science/article/pii/S0022459698978616PublisherArticle
ORCID:
AuthorORCID
Haile, Sossina M.0000-0002-5293-6252
Alternate Title:Structure and Vibrational Spectrum of β-Cs3(HSO4)2[H2−x(P1−x, Sx)O4] (x∼0.5), a New Superprotonic Conductor, and a Comparison with α-Cs3(HSO4)2(H2PO4), Structure and Vibrational Spectrum of β-Cs₃(HSO₄)₂(H₂₋ₓ(P₁₋ₓ, Sx)O₄] (x∼0.5), a New Superprotonic Conductor, and a Comparison with α-Cs₃(HSO₄)₂(H₂PO₄), Structure and Vibrational Spectrum of beta-Cs3(HSO4)2[H2−x(P1−x, Sx)O4] (x∼0.5), a New Superprotonic Conductor, and a Comparison with alpha-Cs3(HSO4)2(H2PO4)
Additional Information:Copyright c1998 by Academic Press. Received 5 December 1997; Accepted 7 April 1998; Available online 8 April 2002. ARTICLE NO. SC987861. 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.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Battelle National LaboratoriesUNSPECIFIED
Electric Power Research Institute (EPRI)UNSPECIFIED
Record Number:CaltechAUTHORS:20131122-151946002
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20131122-151946002
Official Citation:Sossina M. Haile, Pamela M. Calkins, Dane Boysen, Structure and Vibrational Spectrum ofβ-Cs3(HSO4)2[H2−x(P1−x, Sx)O4] (x∼0.5), a New Superprotonic Conductor, and a Comparison withα-Cs3(HSO4)2(H2PO4), Journal of Solid State Chemistry, Volume 139, Issue 2, September 1998, Pages 373-387, ISSN 0022-4596, http://dx.doi.org/10.1006/jssc.1998.7861. (http://www.sciencedirect.com/science/article/pii/S0022459698978616)
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ID Code:42668
Collection:CaltechAUTHORS
Deposited By: Jonathan Gross
Deposited On:26 Nov 2013 23:18
Last Modified:16 Sep 2015 02:24

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