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Title: Investigation of substitution effects and the phase transition in type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2} (1.3<=x<=2.1) using single-crystal X-ray diffraction, Raman spectroscopy, heat capacity and electrical resistivity measurements

Abstract

The substitution of cations in Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2}(1.3<=x<=2.1) is reported. The compounds crystallize at room temperature in the space group la3-bard adopting the type-I clathrate 2x2x2 superstructure with partly ordered framework vacancies (square), whereas at higher temperatures they transform to the primitive, more disordered modification (space group Pm3-barn). The guest atom distributions in the Sn cages on the Rb: Cs ratios is studied by means of single-crystal X-ray diffraction for Rb{sub 2.1(1)}Cs{sub 5.8(1)}Sn{sub 44} at T=293 K (1), Rb{sub 1.42(8)}Cs{sub 6.58(8)}Sn{sub 44} at T=293 K (2a), Rb{sub 1.46(5)}Cs{sub 6.54(5)}Sn{sub 44} at T=373 K (2b) and Rb{sub 1.32(8)}Cs{sub 6.68(8)}Sn{sub 44} at T=293 K (3). The structural order-disorder phase transition influences the electrical resistivity. The hysteresis observed for the electrical resistivity in combination with the symmetric shape of the specific heat anomaly suggests that the transformation is of first-order type and is characterized by an entropy change of about 2.5 J mol{sup -1} K{sup -1}. The Raman spectrum for the low-temperature modification of 2 is also reported. - Graphical Abstract: The effects of substitution of cations in the type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44} (1.3<=x<=2.1) are reported. The distribution of the guests in the Sn cages under different reaction stoichiometriesmore » and annealing times is studied by X-ray diffraction. A structural phase transition in Rb{sub 1.4}Cs{sub 6.6}Sn{sub 44} at 333-363 K affects significantly the electrical resistivity and heat capacity.« less

Authors:
 [1];  [1]; ; ;  [2]; ;  [3]
  1. Technische Universitaet Muenchen, Department Chemie, Lichtenbergstrasse 4, D-85747 Garching (Germany)
  2. University Augsburg, Institute of Physics (Germany)
  3. Department of Materials Science and Technology, Gifu University (Japan)
Publication Date:
OSTI Identifier:
21372368
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 182; Journal Issue: 10; Other Information: DOI: 10.1016/j.jssc.2009.07.034; PII: S0022-4596(09)00343-0; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANNEALING; CESIUM COMPOUNDS; CLATHRATES; ELECTRIC CONDUCTIVITY; ENTROPY; MONOCRYSTALS; ORDER-DISORDER TRANSFORMATIONS; RAMAN SPECTRA; RAMAN SPECTROSCOPY; RUBIDIUM COMPOUNDS; SPACE GROUPS; SPECIFIC HEAT; TEMPERATURE RANGE 0273-0400 K; TIN COMPOUNDS; VACANCIES; X-RAY DIFFRACTION; ALKALI METAL COMPOUNDS; COHERENT SCATTERING; CRYSTAL DEFECTS; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; ELECTRICAL PROPERTIES; HEAT TREATMENTS; LASER SPECTROSCOPY; PHASE TRANSFORMATIONS; PHYSICAL PROPERTIES; POINT DEFECTS; SCATTERING; SPECTRA; SPECTROSCOPY; SYMMETRY GROUPS; TEMPERATURE RANGE; THERMODYNAMIC PROPERTIES

Citation Formats

Kaltzoglou, Andreas, Faessler, Thomas F., E-mail: Thomas.Faessler@lrz.tum.d, Gold, Christian, Scheidt, Ernst-Wilhelm, Scherer, Wolfgang, Kume, Tetsuji, and Shimizu, Hiroyasu. Investigation of substitution effects and the phase transition in type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2} (1.3<=x<=2.1) using single-crystal X-ray diffraction, Raman spectroscopy, heat capacity and electrical resistivity measurements. United States: N. p., 2009. Web. doi:10.1016/j.jssc.2009.07.034.
Kaltzoglou, Andreas, Faessler, Thomas F., E-mail: Thomas.Faessler@lrz.tum.d, Gold, Christian, Scheidt, Ernst-Wilhelm, Scherer, Wolfgang, Kume, Tetsuji, & Shimizu, Hiroyasu. Investigation of substitution effects and the phase transition in type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2} (1.3<=x<=2.1) using single-crystal X-ray diffraction, Raman spectroscopy, heat capacity and electrical resistivity measurements. United States. doi:10.1016/j.jssc.2009.07.034.
Kaltzoglou, Andreas, Faessler, Thomas F., E-mail: Thomas.Faessler@lrz.tum.d, Gold, Christian, Scheidt, Ernst-Wilhelm, Scherer, Wolfgang, Kume, Tetsuji, and Shimizu, Hiroyasu. Thu . "Investigation of substitution effects and the phase transition in type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2} (1.3<=x<=2.1) using single-crystal X-ray diffraction, Raman spectroscopy, heat capacity and electrical resistivity measurements". United States. doi:10.1016/j.jssc.2009.07.034.
@article{osti_21372368,
title = {Investigation of substitution effects and the phase transition in type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2} (1.3<=x<=2.1) using single-crystal X-ray diffraction, Raman spectroscopy, heat capacity and electrical resistivity measurements},
author = {Kaltzoglou, Andreas and Faessler, Thomas F., E-mail: Thomas.Faessler@lrz.tum.d and Gold, Christian and Scheidt, Ernst-Wilhelm and Scherer, Wolfgang and Kume, Tetsuji and Shimizu, Hiroyasu},
abstractNote = {The substitution of cations in Rb{sub x}Cs{sub 8-x}Sn{sub 44}square{sub 2}(1.3<=x<=2.1) is reported. The compounds crystallize at room temperature in the space group la3-bard adopting the type-I clathrate 2x2x2 superstructure with partly ordered framework vacancies (square), whereas at higher temperatures they transform to the primitive, more disordered modification (space group Pm3-barn). The guest atom distributions in the Sn cages on the Rb: Cs ratios is studied by means of single-crystal X-ray diffraction for Rb{sub 2.1(1)}Cs{sub 5.8(1)}Sn{sub 44} at T=293 K (1), Rb{sub 1.42(8)}Cs{sub 6.58(8)}Sn{sub 44} at T=293 K (2a), Rb{sub 1.46(5)}Cs{sub 6.54(5)}Sn{sub 44} at T=373 K (2b) and Rb{sub 1.32(8)}Cs{sub 6.68(8)}Sn{sub 44} at T=293 K (3). The structural order-disorder phase transition influences the electrical resistivity. The hysteresis observed for the electrical resistivity in combination with the symmetric shape of the specific heat anomaly suggests that the transformation is of first-order type and is characterized by an entropy change of about 2.5 J mol{sup -1} K{sup -1}. The Raman spectrum for the low-temperature modification of 2 is also reported. - Graphical Abstract: The effects of substitution of cations in the type-I clathrates Rb{sub x}Cs{sub 8-x}Sn{sub 44} (1.3<=x<=2.1) are reported. The distribution of the guests in the Sn cages under different reaction stoichiometries and annealing times is studied by X-ray diffraction. A structural phase transition in Rb{sub 1.4}Cs{sub 6.6}Sn{sub 44} at 333-363 K affects significantly the electrical resistivity and heat capacity.},
doi = {10.1016/j.jssc.2009.07.034},
journal = {Journal of Solid State Chemistry},
number = 10,
volume = 182,
place = {United States},
year = {Thu Oct 15 00:00:00 EDT 2009},
month = {Thu Oct 15 00:00:00 EDT 2009}
}