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The breaking of a chemical bond is fundamental in most chemical reactions. Tounderstand chemical processes in heterogeneous catalysis or on-surfacepolymerization the study of bond dissociation in molecules adsorbed oncrystalline surfaces is advantageous. Single molecule studies of bond breakingcan give details of the dissociation dynamics, which are challenging to obtainin mole-scale ensemble experiments. Bond breaking in single adsorbed moleculescan be triggered using the energy of the tunnelling electrons in a scanningtunnelling microscope (STM) at selected positions to investigate thedissociation dynamics. Single bond dissociation dynamics has been deeplyinvestigated only in small molecules, but not in larger molecules that exhibitdistinct rotational degrees of freedom. Here, we use low temperature (7 K) STMto dissociate a single bromine atom from an elongated molecule(dibromo-terfluorene) adsorbed on a Ag(111) surface. This rod-like moleculeallows to clearly identify not only displacement of the reaction fragments, butalso their rotation. The results show that the molecular fragment binds to thenearest silver atom and only further rotation is allowed. Moreover, theexcitation responsible for the bond breaking can propagate through themolecular backbone to dissociate a bromine atom that is not located at thepulse position. These results show the important role of the metal substrate inconditioning the bond dissociation dynamics. Our results might allow to improvethe control of the synthesis of 2D materials and targeted engineering ofmolecular architectures.

Bond dissociation dynamics of single molecules on Ag(111)