Computation of the correlated metal-insulator transition in vanadium dioxide from first principles.

Vanadium dioxide (VO2) is a paradigmatic example of a strongly correlated system that undergoes a metal-insulator transition at a structural phase transition. To date, this transition has necessitated significant post hoc adjustments to theory in order to be described properly. Here we report standard state-of-the-art first principles quantum Monte Carlo (QMC) calculations of the structural dependence of the properties of VO2. Using this technique, we simulate the interactions between electrons explicitly, which allows for the metal-insulator transition to naturally emerge, importantly without ad hoc adjustments. The QMC calculations show that the structural transition directly causes the metal-insulator transition and a change in the coupling of vanadium spins. This change in the spin coupling results in a prediction of a momentum-independent magnetic excitation in the insulating state. While two-body correlations are important to set the stage for this transition, they do not change significantly when VO2 becomes an insulator. These results show that it is now possible to account for electron correlations in a quantitatively accurate way that is also specific to materials.