Large Orbital Magnetic Moment in VI 3 .

The existence of the V 3+ -ion orbital moment is an open issue of the nature of magnetism in the van der Waals ferromagnet VI 3 . The huge magnetocrystalline anisotropy in conjunction with the significantly reduced ordered magnetic moment compared to the spin-only value provides strong but indirect evidence of a large V orbital moment. We used the unique capability of X-ray magnetic circular dichroism to determine the orbital component of the total magnetic moment and provide a direct proof of an exceptionally sizable orbital moment of the V 3+ ion in VI 3 . Our ligand field multiplet simulations of the XMCD spectra in synergy with the results of DFT calculations agree with the existence of two V sites with different orbital occupations and OM magnitudes in the ground state.