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Density-Functional Study of the Geometries, Stabilities, and Bond Energies of Group III−V (13−15) Four-Membered-Ring Compounds

Haihong Ni,^† Darrin M. York,^†^‡ Lee Bartolotti,^‡ Richard L. Wells,^† and Weitao Yang*^†

Contribution from the Department of Chemistry, Duke University, Durham, North Carolina 27708-0354, and North Carolina Supercomputing Center, Research Triangle Park, North Carolina 27709-12889

J. Am. Chem. Soc., 1996, 118 (24), pp 5732–5736

DOI: 10.1021/ja951706+

Publication Date (Web): June 19, 1996

†

Duke University.

‡

North Carolina Supercomputing Center.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

A theoretical investigation has been carried out on several group III−V (13−15) four-membered-ring compounds which, if experimentally attainable, are potentially useful as precursors to nanocrystalline electronic and semiconductor materials. Four-membered-ring compounds considered in this study have core structures of the following form: MEM‘E‘ and MEMX (M, M‘ = In, Ga, Al; E, E‘ = P, As; X = Cl, Br). Equilibrium geometries, binding energies, and bond energies were determined based on local density approximation (LDA) and gradient-corrected density-functional methods. Optimized ring geometries obtained with LDA agree closely with single-crystal X-ray crystallographic structures of known compounds with the same four-membered-ring cores. The following trends in bond energies are observed: M−Cl ≫ M−P > M−As ≫ M−Br (M = In, Ga, Al), and Al−Y > Ga−Y > In−Y (Y = P, As, Cl, Br). Although only one M−Br-containing mixed-bridge four-membered-ring compound has been reported and no such Al−Cl-containing mixed-bridge species have yet been synthesized, our calculations suggest that compounds containing these two ring systems are stable.

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