“…Scanning probe microscopy with its high spatial resolution and the ability of single-molecule manipulation is an ideal technique to accomplish this task. For more than three decades, single-atomic and molecular switches have been observed by means of SPM, revealing rotations, − tautomerizations, − and various kinds of bistable configurations. − However, such switching usually consist of one process only, e.g., tautomerization or rotation, and the specific stimuli can individually be identified. For example, the C–H and the CC stretch mode have been shown to excite the rotation of cis -2-butene on the surface of palladium. , In contrast, the excitation of one vibrational mode, which then triggers more than one process hasto the best of our knowledgenot yet been described.…”