Structural, electronic, and magnetic properties of vanadium atom-adsorbed MoSe₂ monolayer

Using the first-principles calculations, we study the structural, electronic, and magnetic properties of vanadium adsorbed MoSe₂ monolayer, and the magnetic couplings between the V adatoms at different adsorption concentrations. The calculations show that the V atom is chemically adsorbed on the MoSe₂ monolayer and prefers the location on the top of an Mo atom surrounded by three nearest-neighbor Se atoms. The interatomic electron transfer from the V to the nearest-neighbor Se results in the polarized covalent bond with weak covalency, associated with the hybridizations of V with Se and Mo. The V adatom induces local impurity states in the middle of the band gap of pristine MoSe₂, and the peak of density of states right below the Fermi energy is associated with the V-dz² orbital. A single V adatom induces a magnetic moment of 5 μ_B that mainly distributes on the V-3d and Mo-4d orbitals. The V adatom is in high-spin state, and its local magnetic moment is associated with the mid-gap impurity states that are mainly from the V-3d orbitals. In addition, the crystal field squashes a part of the V-4s electrons into the V-3d orbitals, which enhances the local magnetic moment. The magnetic ground states at different adsorption concentrations are calculated by generalized gradient approximations (GGA) and GGA+U with enhanced electron localization. In addition, the exchange integrals between the nearest-neighbor V adatoms at different adsorption concentrations are calculated by fitting the first-principle total energies of ferromagnetic (FM) and antiferromagnetic (AFM) states to the Heisenberg model. The calculations with GGA show that there is a transition from ferromagnetic to antiferromagnetic ground state with increasing the distance between the V adatoms. We propose an exchange mechanism based on the on-site exchange on Mo and the hybridization between Mo and V, to explain the strong ferromagnetic coupling at a short distance between the V adatoms. However, the ferromagnetic exchange mechanism is sensitive to both the increased inter-adatom distance at low concentration and the enhanced electron localization by GGA+U, which leads to antiferromagnetic ground state, where the antiferromagnetic superexchange is dominant.