Variation of orbital symmetry of the localized 3d¹ electron of the V⁴⁺ ion upon the metal-insulator transition in VO₂

The electronic structure of the vanadium dioxide VO_2 in the tetragonal R and two monocinic M_1 and M_2 structural modifications was calculated in frames of the local-density functional (LDA) approach and the LSDA + U formalism of correction for correlation effects. Based on the results of calculation, we argue in favor of the Mott-Hubbard mechanism of the metal-insulator transition. It is shown that the transition is accompanied by the change of the orbital in which the 3d^1 electron of the V^{4+} ion is localized. The symmetry of the filled orbital is determined by the local oxygen environment of the vanadium atoms in each structural phase. Depending on the dispersion of the band that corresponds to the orbital occupied, the investigated compound can be either a metal or an insulator.