ESR-STM on diamagnetic molecule: C on graphene.

Electron Spin Resonance-Scanning Tunneling Microscopy (ESR-STM) of C radical ion on graphene is a first demonstration of ESR-STM on diamagnetic molecules. ESR-STM signal at g=2.0±0.1 was measured in accordance with macroscopic ESR of C radical ion. The ESR-STM signal was bias voltage dependent, as it reflects the charge state of the molecule. The signal appears in the bias voltage which enables the ionization of the lowest unoccupied molecular orbital (LUMO) - creation of radical anion, and the highest occupied molecular orbital (HOMO) - creation of a radical cation of the C molecule when it deposited on graphene. In parallel, ESR-STM signal at g=1.7±0.1 was ascribed to Tungsten oxide (WO) at the tip apex. In several experiments, triplet spectrum was observed, and we ascribed their origin to zero-field splitting of doubly ionized CO dimer, as argued in previous ESR experiments of C samples. Second possibility is hyperfine coupling with two C nuclei. In addition, we further validate the interference mechanism previously suggested for ESR-STM noise spectroscopy. The ability of ESR-STM to observe ESR of diamagnetic molecules in parallel with observing their electronic structure, provides a general single molecule identification technique.