Instantaneous band gap collapse in photoexcited monoclinic VO₂ due to photocarrier doping

Using femtosecond time-resolved photoelectron spectroscopy we demonstrate that photoexcitation transforms monoclinic VO₂ quasi-instantaneously into a metal. Thereby, we exclude an 80 fs structural bottleneck for the photoinduced electronic phase transition of VO₂. First-principles many-body perturbation theory calculations reveal a high sensitivity of the VO₂ band gap to variations of the dynamically screened Coulomb interaction, supporting a fully electronically driven isostructural insulator-to-metal transition. We thus conclude that the ultrafast band structure renormalization is caused by photoexcitation of carriers from localized V 3d valence states, strongly changing the screening before significant hot-carrier relaxation or ionic motion has occurred.