Thermally and vibrationally induced tautomerization of single porphycene molecules on a Cu(110) surface
Takashi Kumagai, Felix Hanke, Sylwester Gawinkowski, John Sharp, Konstantinos Kotsis, Jacek Waluk,
Mats Persson, and Leonhard Grill:
We report the direct observation of intramolecular hydrogen atom transfer reactions (tautomerization) within a single porphycene molecule on a Cu(110) surface by scanning tunneling microscopy (STM). It is found that the tautomerization can be induced via inelastic electron tunneling at 5 K. By measuring the bias-dependent tautomerization rate of isotope-substituted molecules, we can assign the STM-induced tautomerization to the excitation of specific molecular vibrations. Furthermore, these vibrations appear as characteristic features in the dI/dV spectra measured over individual molecules. The vibrational modes that are associated with the tautomerization are identified by density functional theory calculations. At higher temperatures above ~75 K, tautomerization is induced thermally and an activation barrier of about 168 meV is determined from an Arrhenius plot.
The original publication is available by link DOI: 10.1103/PhysRevLett.111.246101