Analysis of rich inelastic electron tunneling spectra: case study of terthiophene on Au(111).

Even moderately small molecules like 2,2':5',2"-terthiophene exhibit quite rich vibrational spectra. Detection and assignment of vibronic transitions of such a single adsorbed molecule in inelastic electron tunneling spectroscopy (IETS) using scanning tunneling microscopy are notoriously hampered by noise and the low efficiency of inelastic channels of typically well below 1%. We demonstrate by a thorough statistical analysis that detection of almost all predicted transitions can be determined experimentally within the energy range 0-120 meV with an estimated detection limit for the efficiency of inelastic channels of ∼0.15%. The maximum accuracy of our transition energies is 2 meV and thus smaller than the thermal broadening at 5 K. On short time scales up to some hours, that accuracy appears to be limited by tunneling current noise. The present analysis confirms earlier results which showed that IETS obeys propensity rules rather than selection rules as observed for optical transitions. Furthermore, the previous indications that anharmonic components in the interaction potentials are important for calculating properties of molecular vibrations were corroborated.