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Unusual Sb–Sb bonding in high temperature thermoelectric materials
Author(s) -
Xu Jianxiao,
Kleinke Holger
Publication year - 2008
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20950
Subject(s) - antimonide , antimony , antibonding molecular orbital , thermoelectric materials , crystallography , bismuth , band gap , valence band , materials science , valence (chemistry) , tetrahedrite , fermi level , thermoelectric effect , chalcogen , conduction band , atom (system on chip) , chemistry , atomic orbital , metallurgy , optoelectronics , physics , thermodynamics , galena , pyrite , organic chemistry , quantum mechanics , sphalerite , computer science , embedded system , electron
The emerging families of advanced thermoelectrics are dominated by antimonides and tellurides. Because the structures of the tellurides are mostly composed of NaCl‐related motifs, they do not contain any Te–Te bonds, and all of the antimonide structures exhibit Sb–Sb bonds of various lengths. Taking all Sb–Sb distances shorter than 3.2 Å into account, the Sb atom substructures are Sb 2 4− pairs in β‐Zn 4 Sb 3 , linear Sb 3 7− units in Yb 14 MnSb 11 , planar Sb 4 4− rectangles in the skutterudites, for example, LaFe 3 CoSb 12 , and Sb 8 cubes interconnected via short Sb–Sb bonds to a three‐dimensional network in Mo 3 Sb 5 Te 2 . These interactions have a significant impact on the band gap size as well as on the effective mass around the Fermi level, for the bottom of the conduction band is in all cases predominated by antibonding Sb–Sb interactions, and—in some cases—the top of the valence band by bonding Sb–Sb interactions. © 2008 Wiley Periodicals, Inc. J Comput Chem 2008