Breaking Degeneracy of Tautomerization-Metastability from Days to Seconds.

We present a detailed study of the tautomerization, that is, the switching of hydrogen protons, between different sites in the molecular frame of phthalocyanine (HPc) on a Ag(111) substrate by means of scanning tunneling microscopy (STM) and STM-based pump-and-sample techniques. Our data reveal that the symmetry mismatch between the substrate and the molecular frame lifts the energetic degeneracy of the two HPc tautomers. Their energy difference is so large that only one tautomer can be found in the ground state. Tip-induced tautomerization was triggered at sufficiently high bias voltages. The excited metastable HPc tautomer was found to exhibit a lifetime of at least several days, as derived from the fact that the molecule did not change back to the ground state within experimentally accessible time scales as long as noninvasive tunneling parameters were used to probe the state of the molecule. By the controlled removal of a hydrogen proton from the molecule, a four-level system was created. Pump-and-sample experiments reveal that the lifetime of the metastable positions amounts to seconds only. Current- and bias-dependent studies indicate that the presence of the STM tip modifies the potential barrier, thereby allowing for a controlled tuning of the metastable tautomer's lifetime.