We report the most direct experimental verification of Mott-Hubbard and charge-transfer insulators through x-ray emission spectroscopy in transition-metal (TM) fluorides. The p-d hybridization features in the spectra allow a straightforward energy alignment of the anion-2p and metal-3d valence states, which visually shows the difference between the two types of insulators. Furthermore, in parallel with the theoretical Zaanen-Sawatzky-Allen diagram, a complete experimental systematics of the 3d Coulomb interaction and the 2p-3d charge-transfer energy is reported and could serve as a universal experimental trend for other TM systems including oxides.

Vanadium dioxide is of broad interest as a spin-12 electron system that realizes a metal-insulator transition near room temperature, due to a combination of strongly correlated and itinerant electron physics. Here, resonant inelastic x-ray scattering is used to measure the excitation spectrum of charge and spin degrees of freedom at the vanadium L edge under different polarization and temperature conditions, revealing excitations that differ greatly from those seen in optical measurements. These spectra encode the evolution of short-range energetics across the metal-insulator transition, including the low-temperature appearance of a strong candidate for the singlet-triplet excitation of a vanadium dimer.