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The control and observation of reactants forming a chemical bond at thesingle-molecule level is a longstanding challenge in quantum physics andchemistry. Using a single CO molecule adsorbed at the apex of an atomic forcemicroscope tip together with a Cu(111) surface, the molecular bending isinduced by torques due to van der Waals attraction and Pauli repulsion. As aresult, the vertical force exhibits a characteristic dip-hump evolution withthe molecule-surface separation, which depends sensitively on the initial tiltangle the CO axis encloses with the surface normal. The experimental force dataare reproduced by model calculations that consider the CO deflection in aharmonic potential and the molecular orientation in the Pauli repulsion term ofthe Lennard-Jones potential. The presented findings shed new light onvertical-force extrema that can occur in scanning probe experiments withfunctionalized tips.

Atomic Force Extrema Induced by the Bending of a CO-Functionalized Probe