Tip fuctionalization by atomic manipulation increased the resolution of atomic force microscopy (AFM) and enabled the identification of a priori unknown molecules. Individual molecules are resolved and thus molecular mixtures can be studied molecule by molecule. Combining high-resolution AFM with atomic manipulation we custom-designed molecules by making and breaking bonds with the tip of the microscope and directly characterized the products on the atomic scale. We generated and studied reaction intermediates and investigated chemical reactions trigged by atomic manipulation. We formed diradicals by dissociating halogen atoms and then reversibly triggered ring-opening and -closing reactions via atomic manipulation, allowing us to switch and control the molecule’s reactivity, magnetic and optical properties. Additional information about charge states and charge distributions can be obtained by Kelvin probe force spectroscopy. On multilayer insulating films we investigated single-electron attachment, detachment and transfer between individual molecules.

Radical chemistry and charge manipulation with an atomic force microscope

253rd National Meeting (2017)

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