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Structure and stability of oligomeric anions [M n X3n+ 1]− (M = Al, Ga, In; X = F, Cl, Br, I; n = 2–4): A quantum-chemical study

  • Theoretical Inorganic Chemistry
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Abstract

The structural and thermodynamic properties of oligomeric anions [M n X3n+ 1]− (M = Al, Ga, In; X = F, Cl, Br, I; n = 2, 3, 4) have been obtained by the density functional theory B3LYP method with the LAN2DZ(d) and LAN2DZ(d)+ basis sets. A wide diversity of structural isomers was found for trimeric fluoride anions M3F −10 . Among the trimers, except In3F −10 , the most stable is a linear isomer composed of two MX3 molecules coordinated to the MX −4 anion. The formation of tetrameric anions M4X −13 was demonstrated to be thermodynamically allowed at low temperatures at MX3: X− > 4: 1. The existence of higher oligomers is less probable. The affinity of oligomer halides (MX3) n for halide ions increases with an increase in n. The propensity to form oligomeric anions decreases in the series F > Cl ≥ Br > I. The fluoride systems show a tendency to form structures with CN = 5 and 6, these structures for In being the most stable.

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  1. St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504, Russia

    A. Yu. Timoshkin

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Original Russian Text © A.Yu. Timoshkin, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 87–100.

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Timoshkin, A.Y. Structure and stability of oligomeric anions [M n X3n+ 1]− (M = Al, Ga, In; X = F, Cl, Br, I; n = 2–4): A quantum-chemical study. Russ. J. Inorg. Chem. 54, 86–99 (2009). https://doi.org/10.1134/S0036023609010161

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