Reorientation of a Single Bond within an Adsorbed Molecule by Tunneling Electrons

Scanning tunneling microscopy offers the exciting possibility to manipulate individual molecules by vibrational excitation via inelastically tunneling electrons. The electrons transfer energy into molecular vibrational modes, leading to breakage or formation of individual bonds. It is challenging to precisely control intramolecular changes by this process. We demonstrate that for 4,4'-dihydroxyazobenzene adsorbed on Au(111) or Ag(111), the manipulation facilitates rotation of the OH end groups around the C-O bond between metastable states; this corresponds to a reorientation of the hydrogen, the ultimate limit of a conformational change within a molecule.