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First-principles-based description of VO2 using DFT+DMFT with bond-centered orbitals

Peter Mlkvik, Nicola A. Spaldin, and Claude Ederer*

  • Materials Theory, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 27, 8093 Zürich, Switzerland

  • *Contact author: claude.ederer@mat.ethz.ch
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Phys. Rev. Research 8, 033342 – Published 21 September, 2026

DOI: https://doi.org/10.1103/m911-zsvh

Abstract

We present a combined density-functional theory and dynamical mean-field theory (DFT+DMFT) study of the full structural phase space of rutile-based vanadium dioxide (VO2), including also the less studied M2 and T phases, using an unconventional bond-centered orbital basis. The use of bond-centered orbitals allows us to treat all main phases of VO2, and the structural transitions between them, using one consistent approach with moderate computational cost and without prepattering of the structure into dimerized and undimerized V-V pairs. We obtain two distinct insulating states on the two different types of vanadium chains in the M2 phase, a singlet insulator on the dimerized chains and a Mott insulator on the zigzag-distorted chains, which, however, are strongly coupled in the M2 phase and thus the metal-insulator transition always occurs concomitantly for both types of sites. We also demonstrate that the M2 phase corresponds to a local energy minimum in the structural phase space of VO2, the stability of which, apart from the internal structural distortion, depends crucially on the unit cell strain relative to the undistorted rutile phase. Our calculations further indicate that the symmetry-distinct triclinic T phase corresponds electronically to either an M1- or an M2-type insulator with an abrupt transition as a function of distortion. Finally, we disentangle the effect of the dimerization and zigzag distortions by constructing hypothetical structures that contain only one site type, finding that the zigzag distortion strongly favors emergence of the Mott-insulating state, as a function of both distortion and on-site interaction.

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Phys. Rev. Research 8, 033342– Published 21 September, 2026
  • Received 17 April 2026
  • Accepted 27 August 2026
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