Search for: All records

Abstract Electronic structure and magnetic interactions of a Tb adatom on graphene are investigated from first principles using combination of density functional theory and multiconfigurational quantum chemistry techniques including spin–orbit coupling (SOC) . We determine that the six-fold symmetry hollow site is the preferred adsorption site and investigate electronic spectrum for different adatom oxidation states including Tb³⁺, Tb²⁺, Tb¹⁺, and Tb⁰. For all charge states, the Tb $4f^8$configuration is retained with other adatom valence electrons being distributed over $5d_{xy}$, $5d_{x2+y2}$, and $6s/5d_0$single-electron orbitals. We find strong intra-site adatom exchange coupling that ensures that the $5d6s$spins are parallel to the4fspin. For Tb³⁺, the energy levels can be described by theJ = 6 multiplet split by the graphene crystal field (CF). For other oxidation states, the interaction of4felectrons with spin and orbital degrees of freedom of $6s5d$electrons in the presence of SOC results in the low-energy spectrum composed closely lying effective multiplets that are split by the graphene CF. Stable magnetic moment is predicted for Tb³⁺and Tb²⁺adatoms due to uniaxial magnetic anisotropy and effective anisotropy barrier around 440 cm⁻¹controlled by the temperature assisted quantum tunneling of magnetization through the third excited doublet. On the other hand, in-plane magnetic anisotropy is found for Tb¹⁺and Tb⁰adatoms. Our results indicate that the occupation of the $6s5d$orbitals can dramatically affect the magnetic anisotropy and magnetic moment stability of rare earth adatoms.