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Author Devlin, Kasey P. ♦ Glaid, Andrew J. ♦ Brant, Jacilynn A. ♦ Zhang, Jian-Han ♦ Srnec, Matthew N. ♦ Clark, Daniel J. ♦ Soo Kim, Yong ♦ Jang, Joon I. ♦ Daley, Kimberly R. ♦ Moreau, Meghann A. ♦ Madura, Jeffry D. ♦ Aitken, Jennifer A.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ ABSORPTION ♦ COBALT ♦ DENSITY ♦ DENSITY FUNCTIONAL METHOD ♦ ELECTRONIC STRUCTURE ♦ GROUND STATES ♦ HARMONIC GENERATION ♦ LITHIUM ♦ MIXTURES ♦ MONOCRYSTALS ♦ ORTHORHOMBIC LATTICES ♦ POWDERS ♦ SEMICONDUCTOR MATERIALS ♦ SILICATES ♦ SOLIDS ♦ SPACE GROUPS ♦ SULFIDES ♦ SYNTHESIS ♦ X RADIATION ♦ X-RAY DIFFRACTION
Abstract High-temperature, solid-state synthesis in the Li{sub 2}MnSnS{sub 4} system led to the discovery of two new polymorphic compounds that were analyzed using single crystal X-ray diffraction. The α-polymorph crystallizes in Pna2{sub 1} with the lithium cobalt (II) silicate, Li{sub 2}CoSiO{sub 4}, structure type, where Z=4, R1=0.0349 and wR2=0.0514 for all data. The β-polymorph possesses the wurtz-kesterite structure type, crystallizing in Pn with Z=2, R1=0.0423, and wR2=0.0901 for all data. Rietveld refinement of synchrotron X-ray powder diffraction was utilized to quantify the phase fractions of the polymorphs in the reaction products. The α/β-Li{sub 2}MnSnS{sub 4} mixture exhibits an absorption edge of ∼2.6–3.0 eV, a wide region of optical transparency in the mid- to far-IR, and moderate SHG activity over the fundamental range of 1.1–2.1 μm. Calculations using density functional theory indicate that the ground state energies and electronic structures for α- and β-Li{sub 2}MnSnS{sub 4}, as well as the hypothetical polymorph, γ-Li{sub 2}MnSnS{sub 4} with the wurtz-stannite structure type, are highly similar. - Graphical abstract: Two polymorphs, α- and β-Li{sub 2}MnSnS{sub 4}, have been discovered using single crystal X-ray diffraction. Rietveld refinement of synchrotron X-ray powder diffraction data indicates the presence of both polymorphs in the samples that were analyzed. - Highlights: • Li{sub 2}MnSnS{sub 4} exists as two polymorphs crystallizing in the Pna2{sub 1} and Pn space groups. • The α- and β-Li{sub 2}MnSnS{sub 4} mixture exhibits a moderate SHG response over a broad range. • The α- and β-Li{sub 2}MnSnS{sub 4} mixture exhibits an optical absorption edge of ∼2.6–3.0 eV. • Synchrotron powder diffraction data are necessary to distinguish α- and β-Li{sub 2}MnSnS{sub 4.} • Electronic structure calculations show similar total energies for α- and β-Li{sub 2}MnSnS{sub 4}.
ISSN 00224596
Educational Use Research
Learning Resource Type Article
Publisher Date 2015-11-15
Publisher Place United States
Journal Journal of Solid State Chemistry
Volume Number 231


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