Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)

Baranets, Sviatoslav A.; Childs, Amanda B.; He, Hua; Bobev, Svilen

doi:10.3390/cryst10040298

Title: Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A₈Ga_xSn_46–x (A = Rb, Cs; 6.9 < x < 7.5)

Journal Article · Mon Apr 13 00:00:00 EDT 2020 · Crystals

DOI:https://doi.org/10.3390/cryst10040298· OSTI ID:1697974

^[1]; Childs, Amanda B. ^[1]; He, Hua ^[1];

^[1]

Univ. of Delaware, Newark, DE (United States)

Exploratory studies in the systems Rb–Ga–Sn and Cs–Ga–Sn yielded the cubic type-I clathrates with refined compositions Rb₈Ga_xSn_46–x and Cs₈Ga_xSn_46–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 Rb₈Ga_xSn_46–x and Cs₈Ga_xSn_46–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, Rb₈Ga_xSn_46–x and Cs₈Ga_xSn_46–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 A₈Sn_46–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 A₈Ga_xSn_46–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.

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Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008885

OSTI ID:: 1697974

Journal Information:: Crystals, Vol. 10, Issue 4; ISSN 2073-4352

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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CSD 1989526: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s88h The current record is supplemented by this dataset	dataset	January 2020
CSD 1989527: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s89j The current record is supplemented by this dataset	dataset	January 2020
CSD 1989528: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s8bk The current record is supplemented by this dataset	dataset	January 2020
CSD 1989529: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s8cl The current record is supplemented by this dataset	dataset	January 2020
CSD 1989530: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s8dm The current record is supplemented by this dataset	dataset	January 2020
CSD 1989531: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s8fn The current record is supplemented by this dataset	dataset	January 2020
CSD 1989532: Experimental Crystal Structure Determination A., Baranets, Sviatoslav; B., Childs, Amanda; Hua, He, https://doi.org/10.25505/fiz.icsd.cc24s8gp The current record is supplemented by this dataset	dataset	January 2020

Title: Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)

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Title: Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A₈Ga_xSn_46–x (A = Rb, Cs; 6.9 < x < 7.5)