Evidence of exciton-libron coupling in chirally adsorbed single molecules

Vibronic coupling in molecules plays an essential role in photophysics. Here, the authors observe optical fingerprints of the coupling between librational states and charged excited states in a single phthalocyanine molecule chirally absorbed on a surface. Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using mu eV-resolved tip-enhanced spectroscopy.

Automated summary

The authors observed the coupling between librational states and charged excited states in a phthalocyanine molecule absorbed on a surface. They provided a detailed analysis of the coupling and successfully simulated the spectral features. This research showcases the potential of using low-energy molecular modes to characterize molecular dynamics.