Nano-Scale Manipulation of Single-Molecule Conformational Transition Through Vibrational Excitation

On-demand control of molecular actions is a crucial step toward the realization of single-molecule functional devices. Such a control can be achieved by manipulating interactions between individual molecules and their nanoscale environment. In this study, we induce and manipulate the conformational transition of a single molecular adsorbate by exciting its vibrations with tunneling electrons using scanning tunneling microscopy. Several transition pathways between two structural states of a pyrrolidine molecule on a Cu(100) surface have been identified as being driven by different molecular vibrations. Density functional theory simulations further determine the nuclear motions of these vibrational modes. The introduction of tip-induced van der Waals forces and intermolecular interactions allows for precise manipulation of the molecule-environment interaction, which shifts the vibrational energies and alters the transition probability through different channels between the two structural states. This work reveals how molecular conformational transitions can be modulated by external force fields in a tunable nano-cavity, highlighting the potential to deliberately engineer molecule-environment interactions for specific molecular functions.