The Metal-Insulator Transition of NbO2: an Embedded Peierls Instability

Results of first principles augmented spherical wave electronic structure calculations for niobium dioxide are presented. Both metallic rutile and insulating low-temperature NbO2, which crystallizes in a distorted rutile structure, are correctly described within density functional theory and the local density approximation. Metallic conductivity is carried to equal amounts by metal t_{2g} orbitals, which fall into the one-dimensional d_parallel band and the isotropically dispersing e_{g}^{pi} bands. Hybridization of both types of bands is almost negligible outside narrow rods along the line X--R. In the low-temperature phase splitting of the d_parallel band due to metal-metal dimerization as well as upshift of the e_{g}^{pi} bands due to increased p-d overlap remove the Fermi surface and open an optical band gap of about 0.1 eV. The metal-insulator transition arises as a Peierls instability of the d_parallel band in an embedding background of e_{g}^{pi} electrons. This basic mechanism should also apply to VO2, where, however, electronic correlations are expected to play a greater role due to stronger localization of the 3d electrons.