Electric-Field Control of a Single-Atom Polar Bond.

We expose the polar covalent bond between a single Au atom terminating the apex of an atomic force microscope tip and a C atom of graphene on SiC(0001) to an external electric field. For one field orientation, the Au─C bond is strong enough to sustain the mechanical load of partially detached graphene, while for the opposite orientation, the bond breaks easily. Calculations based on density-functional theory and nonequilibrium Green's function methods support the experimental observations by unveiling bond forces that reflect the polar character of the bond. Field-induced charge transfer between the atomic orbitals modifies the polarity of the different electronegative reaction partners and the Au─C bond strength.