AbstractThe 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 Sb24− pairs in β‐Zn4Sb3, linear Sb37− units in Yb14MnSb11, planar Sb44− rectangles in the skutterudites, for example, LaFe3CoSb12, and Sb8 cubes interconnected via short Sb–Sb bonds to a three‐dimensional network in Mo3Sb5Te2. 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