Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)
Abstract
Exploratory studies in the systems Rb–Ga–Sn and Cs–Ga–Sn yielded the cubic type-I clathrates with refined compositions Rb8GaxSn46–x and Cs8GaxSn46–x (6.9 < x < 7.5). Nearly single-phase materials with good crystallinity were obtained from stoichiometric reactions of the elements. The structures were characterized by means of single-crystal X-ray diffraction methods. Both Rb8GaxSn46–x and Cs8GaxSn46–x represents cases, where a Group 13 element randomly substitutes a Group 14 element in the structure. The extent of Ga/Sn mixing is apparently governed by the drive of the system to achieve an optimal valence electron count, and hence, Rb8GaxSn46–x and Cs8GaxSn46–x (x ≈ 8) can be regarded as Zintl phases. This notion is supported by structure refinements on a multitude of single-crystal X-ray diffraction data, which also confirm that both types of cages in the cubic type-I structure are fully occupied by Rb and Cs atoms. The open-framework, comprised of 46 nodes per formula unit, adapts to the incorporation of nearly eight Ga atoms within the matrix of Sn, whereby small, short-range distortions result. The exact nature of these effects is still unclear, as so far, the structural variations could only be modeled as both positional and occupational disorder at one of three framework sites. Sincemore »
- Publication Date:
- Research Org.:
- Univ. of Delaware, Newark, DE (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1697974
- Grant/Contract Number:
- SC0008885
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Crystals
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 2073-4352
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; clathrates; type-I structure; Zintl phases; crystal structures
Citation Formats
Baranets, Sviatoslav A., Childs, Amanda B., He, Hua, and Bobev, Svilen. Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5). United States: N. p., 2020.
Web. doi:10.3390/cryst10040298.
Baranets, Sviatoslav A., Childs, Amanda B., He, Hua, & Bobev, Svilen. Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5). United States. https://doi.org/10.3390/cryst10040298
Baranets, Sviatoslav A., Childs, Amanda B., He, Hua, and Bobev, Svilen. Mon .
"Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)". United States. https://doi.org/10.3390/cryst10040298. https://www.osti.gov/servlets/purl/1697974.
@article{osti_1697974,
title = {Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)},
author = {Baranets, Sviatoslav A. and Childs, Amanda B. and He, Hua and Bobev, Svilen},
abstractNote = {Exploratory studies in the systems Rb–Ga–Sn and Cs–Ga–Sn yielded the cubic type-I clathrates with refined compositions Rb8GaxSn46–x and Cs8GaxSn46–x (6.9 < x < 7.5). Nearly single-phase materials with good crystallinity were obtained from stoichiometric reactions of the elements. The structures were characterized by means of single-crystal X-ray diffraction methods. Both Rb8GaxSn46–x and Cs8GaxSn46–x represents cases, where a Group 13 element randomly substitutes a Group 14 element in the structure. The extent of Ga/Sn mixing is apparently governed by the drive of the system to achieve an optimal valence electron count, and hence, Rb8GaxSn46–x and Cs8GaxSn46–x (x ≈ 8) can be regarded as Zintl phases. This notion is supported by structure refinements on a multitude of single-crystal X-ray diffraction data, which also confirm that both types of cages in the cubic type-I structure are fully occupied by Rb and Cs atoms. The open-framework, comprised of 46 nodes per formula unit, adapts to the incorporation of nearly eight Ga atoms within the matrix of Sn, whereby small, short-range distortions result. The exact nature of these effects is still unclear, as so far, the structural variations could only be modeled as both positional and occupational disorder at one of three framework sites. Since vacancies in the structures of the binary type-I clathrates A8Sn46–x x (A = Rb, Cs; = missing Sn atom) are also known to cause local distortions, the latter were also synthesized with the same protocols used for the synthesis of A8GaxSn46–x and structurally re-analyzed. The results from the latter studies confirm that homogeneity issues abound, and that the final structures/compositions are an intricate function of the experimental conditions.},
doi = {10.3390/cryst10040298},
journal = {Crystals},
number = 4,
volume = 10,
place = {United States},
year = {Mon Apr 13 00:00:00 EDT 2020},
month = {Mon Apr 13 00:00:00 EDT 2020}
}
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