The Si(111)7×7 surface exposed to 0.1L of O 2 and the carbonized Si(111) surface are investigated by electron spin resonance scanning tunneling microscopy (ESR-STM) using frequency sweeps and magnetic field sweeps. Only after oxidizing the clean Si(111)7×7 or by using the carbonized Si(111), spatially averaged ESR-STM spectra exhibit several peaks and dips around the frequencies corresponding to g=2. The energy difference between these features is close to the known hyperfine splitting of A≅9MHz for vacancies in SiC interacting with next-nearest neighbor 29 Si. Such spectra with peaks and dips can be qualitatively reproduced by introducing a primary encounter of the lead electrons with the localized spin correlating the two spins which afterwards evolve in different local hyperfine fields, thus, developing a relative spin angle prior to tunneling.