Unveiling the Decisive Factor for the Sharp Transition in the Scanning Tunneling Spectroscopy of a Single Nickelocene...

Scanning tunneling microscopy (STM) has been utilized to realize the precise measurement and control of local spin states. Experiments have demonstrated that when a nickelocene (Nc) molecule is attached to the apex of an STM tip, the dI/dV spectra exhibit a sharp or a smooth transition when the tip is displaced toward the substrate. However, what leads to the two distinct types of transitions remains unclear, and more intriguingly, the physical origin of the abrupt change in the line shape of dI/dV spectra remains unclear. To clarify these intriguing issues, we perform first-principles-based simulations on the STM tip control process for the Cu tip/Nc/Cu(100) junction. In particular, we find that the suddenly enhanced hybridization between the d orbitals on the Ni ion and the metallic bands in the substrate leads to Kondo correlation overwhelming spin excitation, which is the main cause of the sharp transition in the dI/dV spectra observed experimentally.