A theoretical study of the dependence of the ASxSi6−x cluster structures and properties on composition

The effect of the composition ratio between arsenic and silicon atoms on the structures and properties of As_xSi_6?x (x = 0–6) have been systematically investigated using the density functional theory at the B3LYP/6‐311+G* level. The As_xSi_6?x clusters prefer substitutional rather than attaching structures; the Si‐rich clusters favor Si₆‐like structures, whereas the As‐rich clusters prefer As₆‐like structures. The As atoms locating at the framework may explain the difficulty of removal of arsenic impurities from polycrystalline silicon. In general, the average binding energies gradually decrease, implying the As_xSi_6?x clusters become increasingly unstable as x increases. Both the HOMO‐LUMO gaps and the As‐dissociation energies present a strong even–odd alternation, implying alternating chemical stability, with the even x members being more stable than the odd ones. The dissociation energies of an As atom from As_xSi_6?x are: 3.07, 2.84, 1.84, 2.52, 1.86, and 2.85 eV, for x = 1–6, respectively, and 3.80, 3.08, 2.64, 3.01, 2.93, 3.16 eV for Si (x = 0–5). These dissociation energy results should provide a useful reference for further experimental investigations. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012