Influence of Orbital Character on the Ground State Electronic Properties in the van Der Waals Transition Metal Iodides VI(3) and CrI(3)

[Image: see text] Two-dimensional van der Waals magnetic semiconductors display emergent chemical and physical properties and hold promise for novel optical, electronic and magnetic “few-layers” functionalities. Transition-metal iodides such as CrI(3) and VI(3) are relevant for future electronic and spintronic applications; however, detailed experimental information on their ground state electronic properties is lacking often due to their challenging chemical environment. By combining X-ray electron spectroscopies and first-principles calculations, we report a complete determination of CrI(3) and VI(3) electronic ground states. We show that the transition metal-induced orbital filling drives the stabilization of distinct electronic phases: a wide bandgap in CrI(3) and a Mott insulating state in VI(3). Comparison of surface-sensitive (angular-resolved photoemission spectroscopy) and bulk-sensitive (X-ray absorption spectroscopy) measurements in VI(3) reveals a surface-only V(2+) oxidation state, suggesting that ground state electronic properties are strongly influenced by dimensionality effects. Our results have direct implications in band engineering and layer-dependent properties of two-dimensional systems.