The metal‐insulator transitions of VO2: A band theoretical approach

Abstract The results of first principles electronic structure calculations for the metallic rutile and the insulating monoclinic phase of vanadium dioxide are presented. In addition, the insulating phase is investigated for the first time. The density functional calculations allow for a consistent understanding of all three phases. In the rutile phase metallic conductivity is carried by metal orbitals, which fall into the one‐dimensional band, and the isotropically dispersing bands. Hybridization of both types of bands is weak. In the phase splitting of the band due to metal‐metal dimerization and upshift of the bands due to increased p ‐ d overlap lead to an effective separation of both types of bands. Despite incomplete opening of the optical band gap due to the shortcomings of the local density approximation, the metal‐insulator transition can be understood as a Peierls‐like instability of the band in an embedding background of electrons. In the phase, the metal‐insulator transition arises as a combined embedded Peierls‐like and antiferromagnetic instability. The results for VO 2 fit into the general scenario of an instability of the rutile‐type transition‐metal dioxides at the beginning of the d series towards dimerization or antiferromagnetic ordering within the characteristic metal chains. This scenario was successfully applied before to MoO 2 and NbO 2 . In the compounds, the and bands can be completely separated, which leads to the observed metal‐insulator transitions.