Variable Charge State, Magnetic Excitations, and Kondo Effect of Sm/g/Ir(111)
Using low-temperature scanning tunneling microscopy we investigate the charge state, magnetic excitations, and Kondo features of individual Sm adatoms on graphene/Ir(111). Depending on the number and distance of their neighbors, Sm atoms can be in two discrete charge states. At certain distances, a reversible transition between these two states is induced by the electric field of the STM tip leading to concentric charge rings in the images. Only atoms in one of the two charge states exhibit magnetic excitations in d$I$/d$V$ spectra. Two such excitations are located at 35~meV and 54~meV and related to transitions from the $J = 1/2$ ground state doublet to the first crystal field split $J = 3/2$ multiplet. Together with the intra-atomic exchange excitations at higher energy, these observations indicate that Sm transfers one $6s$ electron to the substrate while it retains its gas-phase $4f$ filling. New for lanthanide adatoms, we observe a Kondo resonance. The Zeeman splitting of the Kondo peak reveals that Sm retains its large gas-phase $g$-factor. Comparison of d$I$/d$V$ spectra to cotunneling theory yields the crystal field acting on the $4f$ shell and, consequently, on the $J = 3/2$ quadruplet, confirms Sm$^+$ as the ground state, and identifies Sm$^{2+}$ as being energetically close, thereby rationalizing our observation of variable charge states.