Synthesis, Crystal Structure, and Electronic Structure of InCdBr3

✍ Scribed by Richard Dronskowski

• Publisher: Elsevier Science
• Year: 1995
• Tongue: English
• Weight: 408 KB
• Volume: 116
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1995.1180

✦ Synopsis

Colorless crystals of diamagnetic (\mathrm{InCdBr}{3}) are synthesized from elemental (\mathrm{Cd}) in an (\mathrm{InBr}{3}) melt. The new phase crystallizes in the orthorhombic (\mathrm{NH}{4} \mathrm{CdCl}{3}) structure type ((a=944.7(2) \mathrm{pm}, b=) 410.47(8) pm, (c=1545.5(3) \mathrm{pm}, P n m a), and (Z=4) ). (\mathrm{Cd}^{2+}) is octahedrally coordinated by (\mathrm{Br}^{-})anions whereas the monovalent (\mathbf{I n}^{+})cation is located in a strongly distorted trigonal (\mathrm{Br}^{-})prism, tricapped by other (\mathrm{Br}^{-})anions. Semiempirical band structure calculations (CSC-EH-TB) show moderately strong covalent contributions to (\mathrm{In}^{+}-\mathrm{Br}^{-})bonding, similar to those found in the binary In/Br crystal chemical system. The quality of the semiempirical calculations is compared in detail with (a b) initio band structure computations (TB-LMTO-ASA). Valence charge density plots based on the latter disprove the existence of a directed electron "lone-pair" residing on monovalent (\mathrm{In}^{+}). O 1995 Academic Press, Inc.