Abstract
A quantum-mechanical calculation of the relative stability, structural parameters, and vibrational frequencies of V2O3 molecule isomers for different spin states was carried out using the BPW91/6-311+G(d, p) method. It was shown that the isomer with the C s structure (nonplanar VOVO rectangle with an O atom attached to it) in the X 5 A″ electronic state possesses the maximum stability. The energy of the C 2v symmetry structure was higher than the lowest energy by just 23 cm−1. It definitely indicated the impossibility of usage of the harmonic model in order to calculate the thermodynamic functions of V2O3 (g). A model is proposed based on which the energy levels and vibrational sums of states for this type of motion were calculated for the C s → C 2v → C s transition coordinate. These data, as well as results obtained from quantum-mechanical calculations, were used to calculate the thermodynamic functions of V2O3 (g) in the temperature range of T = 100–6000 K. The calculations were performed with the five excited electronic states with energies from 1000 to 9000 cm−1 taken into account. A comparison with the data calculated in the “rigid rotator-harmonic oscillator” approximation was performed.
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Original Russian Text © A.V. Gusarov, E.L. Osina, 2012, published in Teplofizika Vysokikh Temperatur, 2012, Vol. 50, No. 1, pp. 60–64.
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Gusarov, A.V., Osina, E.L. Anharmonicity in the V2O3 molecule and thermodynamic properties of V2O3 in the gas phase. High Temp 50, 56–60 (2012). https://doi.org/10.1134/S0018151X12010075
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DOI: https://doi.org/10.1134/S0018151X12010075