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Systematic theoretical studies of the [XMYH]n, inorganic rings and clusters (M = Al, Ga, In; Y = N, P, As; X = H, F, Cl, Br, I; n = 1-6) have been carried out using hybrid Hartree-Fock density functional theory. A consistent set of the structural and thermodynamic properties has been obtained. The stability of the MY bond decreases in the order Al > Ga ≥ In; N ≫ P > As. Terminal groups X have a minor influence on the subsequent elimination enthalpies of the clusters. In the case of X = H, hydrogen elimination makes formation of the [HMYH]6 oligomers from MH 3 and YH3 thermodynamically favorable; while in the case of halide substituents, formation of [XMYH]6 is thermodynamically unfavorable, except for the system with the strongest MY bond (AIN). Substitution of the acidic hydrogen by X is favorable energetically for all [HMYH]6 clusters, but is complicated by the processes of cluster destruction to form the [X2MYH2]2 dimers. The high stability of the [HMNH]6 clusters makes them attractive single-source precursors for the production of 13-15 composites.
Original language | English |
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Pages (from-to) | 3080-3089 |
Number of pages | 10 |
Journal | Inorganic Chemistry |
Volume | 43 |
Issue number | 10 |
DOIs | |
State | Published - 17 May 2004 |
ID: 17373365