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Title: Ternary lanthanum sulfide selenides {alpha}-LaS{sub 2-x}Se{sub x} (0<x<2) with mixed dichalcogenide anions X{sub 2}{sup 2-} (X=S, Se)

Abstract

Mixed lanthanum sulfide selenides LaS{sub 2-x}Se{sub x} (0<x<2) were obtained by metathesis reactions starting from anhydrous lanthanum chloride and alkali metal polychalcogenides. The LaS{sub 2-x}Se{sub x} compounds crystallize in space group P2{sub 1}/a, no. 14, and adopt the {alpha}-LnS{sub 2} (Ln=Y, La-Lu) structure type with a pronounced site preference for the chalcogen atoms. The mixed chalcogenides form a complete miscible series with lattice parameters a=820-849 pm, b=413-425 pm and c=822-857 pm ({beta} Almost-Equal-To 90 Degree-Sign) following Vegard's rule. Raman signals indicate the presence of mixed X{sub 2}{sup 2-} dianions, a species rarely evidenced in literature, besides the well known anions S{sub 2}{sup 2-} and Se{sub 2}{sup 2-}. The band gaps of the LaS{sub 2-x}Se{sub x} compounds, determined by optical spectroscopy, decrease nearly linearly with increasing amount of selenium. - Graphical abstract: Raman spectra and site occupancies in the structures of selected lanthanum sulfide selenides. Highlights: Black-Right-Pointing-Pointer Vegard series of mixed lanthanum sulfide selenides LaS{sub 2-x}Se{sub x} (0<x<2). Black-Right-Pointing-Pointer Pronounced site ordering of chalcogen positions. Black-Right-Pointing-Pointer Optical band gaps decrease with Se content. Black-Right-Pointing-Pointer Raman measurements evidence mixed X{sub 2}{sup 2-} dimeric anions.

Authors:
 [1];  [1]
  1. Department of Chemistry and Food Chemistry, Technische Universitaet Dresden, D-01062 Dresden (Germany)
Publication Date:
OSTI Identifier:
21612857
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 185; Other Information: DOI: 10.1016/j.jssc.2011.10.039; PII: S0022-4596(11)00581-0; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKALI METALS; ANIONS; LANTHANUM CHLORIDES; LANTHANUM SULFIDES; LATTICE PARAMETERS; MONOCLINIC LATTICES; RAMAN SPECTRA; RARE EARTHS; SELENIDES; SELENIUM; SIGNALS; SPACE GROUPS; SPECTROSCOPY; CHALCOGENIDES; CHARGED PARTICLES; CHLORIDES; CHLORINE COMPOUNDS; CRYSTAL LATTICES; CRYSTAL STRUCTURE; ELEMENTS; HALIDES; HALOGEN COMPOUNDS; IONS; LANTHANUM COMPOUNDS; LANTHANUM HALIDES; METALS; RARE EARTH COMPOUNDS; SELENIUM COMPOUNDS; SEMIMETALS; SPECTRA; SULFIDES; SULFUR COMPOUNDS; SYMMETRY GROUPS

Citation Formats

Bartsch, Christian, and Doert, Thomas. Ternary lanthanum sulfide selenides {alpha}-LaS{sub 2-x}Se{sub x} (0<x<2) with mixed dichalcogenide anions X{sub 2}{sup 2-} (X=S, Se). United States: N. p., 2012. Web. doi:10.1016/j.jssc.2011.10.039.
Bartsch, Christian, & Doert, Thomas. Ternary lanthanum sulfide selenides {alpha}-LaS{sub 2-x}Se{sub x} (0<x<2) with mixed dichalcogenide anions X{sub 2}{sup 2-} (X=S, Se). United States. https://doi.org/10.1016/j.jssc.2011.10.039
Bartsch, Christian, and Doert, Thomas. Sun . "Ternary lanthanum sulfide selenides {alpha}-LaS{sub 2-x}Se{sub x} (0<x<2) with mixed dichalcogenide anions X{sub 2}{sup 2-} (X=S, Se)". United States. https://doi.org/10.1016/j.jssc.2011.10.039.
@article{osti_21612857,
title = {Ternary lanthanum sulfide selenides {alpha}-LaS{sub 2-x}Se{sub x} (0<x<2) with mixed dichalcogenide anions X{sub 2}{sup 2-} (X=S, Se)},
author = {Bartsch, Christian and Doert, Thomas},
abstractNote = {Mixed lanthanum sulfide selenides LaS{sub 2-x}Se{sub x} (0<x<2) were obtained by metathesis reactions starting from anhydrous lanthanum chloride and alkali metal polychalcogenides. The LaS{sub 2-x}Se{sub x} compounds crystallize in space group P2{sub 1}/a, no. 14, and adopt the {alpha}-LnS{sub 2} (Ln=Y, La-Lu) structure type with a pronounced site preference for the chalcogen atoms. The mixed chalcogenides form a complete miscible series with lattice parameters a=820-849 pm, b=413-425 pm and c=822-857 pm ({beta} Almost-Equal-To 90 Degree-Sign) following Vegard's rule. Raman signals indicate the presence of mixed X{sub 2}{sup 2-} dianions, a species rarely evidenced in literature, besides the well known anions S{sub 2}{sup 2-} and Se{sub 2}{sup 2-}. The band gaps of the LaS{sub 2-x}Se{sub x} compounds, determined by optical spectroscopy, decrease nearly linearly with increasing amount of selenium. - Graphical abstract: Raman spectra and site occupancies in the structures of selected lanthanum sulfide selenides. Highlights: Black-Right-Pointing-Pointer Vegard series of mixed lanthanum sulfide selenides LaS{sub 2-x}Se{sub x} (0<x<2). Black-Right-Pointing-Pointer Pronounced site ordering of chalcogen positions. Black-Right-Pointing-Pointer Optical band gaps decrease with Se content. Black-Right-Pointing-Pointer Raman measurements evidence mixed X{sub 2}{sup 2-} dimeric anions.},
doi = {10.1016/j.jssc.2011.10.039},
url = {https://www.osti.gov/biblio/21612857}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 185,
place = {United States},
year = {2012},
month = {1}
}