Anisotropic Hyperfine Interaction of Surface-Adsorbed Single Atoms

[Image: see text] Hyperfine interactions have been widely used in material science, organic chemistry, and structural biology as a sensitive probe to local chemical environments. However, traditional ensemble measurements of hyperfine interactions average over a macroscopic number of spins with different geometrical locations and nuclear isotopes. Here, we use a scanning tunneling microscope (STM) combined with electron spin resonance (ESR) to measure hyperfine spectra of hydrogenated-Ti on MgO/Ag(100) at low-symmetry binding sites and thereby determine the isotropic and anisotropic hyperfine interactions at the single-atom level. Combining vector-field ESR spectroscopy with STM-based atom manipulation, we characterize the full hyperfine tensors of (47)Ti and (49)Ti and identify significant spatial anisotropy of the hyperfine interactions for both isotopes. Density functional theory calculations reveal that the large hyperfine anisotropy arises from highly anisotropic distributions of the ground-state electron spin density. Our work highlights the power of ESR-STM-enabled single-atom hyperfine spectroscopy in revealing electronic ground states and atomic-scale chemical environments.