Abstract

The monoclinic (space group C2/m) superstructure of the suboxide V14O6, which is formed as a result of the atomic and vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is investigated using X-ray diffraction and symmetry analysis. The monoclinic suboxide V14O6 is observed in the vanadium oxide samples VO0.57, VO0.81, and VO0.86 synthesized at 1770 K and the samples VOy (0.87 ≤ y ≤ 0.98) additionally annealed at 1470 K after the synthesis. It is established that the channel of the disorder-order phase transition associated with the formation of the monoclinic suboxide V14O6 includes six superstructure vectors belonging to three non-Lifshitz stars of one type {k1}. The distribution function of the oxygen atoms in the monoclinic superstructure of the suboxide V14O6 is calculated. It is demonstrated that the displacements of vanadium atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the facecentered cubic sublattice and the transition from the suboxide V14O6 to the cubic vanadium monoxide with the B1 structure.

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