Interactions between molecular electronic and vibrational states manifest themselves in a variety of forms and have a strong impact on molecular physics and chemistry. For example, the efficiency of energy transfer between organic molecules, ubiquitous in biological systems and in organic optoelectronics, is strongly influenced by vibronic coupling. Using an approach based on scanning tunneling microscope-induced luminescence (STML), we reveal vibronic interactions in optical spectra of a series of single phthalocyanine derivative molecules featuring degenerate or near-degenerate excited states. Based on detailed theoretical simulations, we disentangle spectroscopic signatures belonging to Franck-Condon and Herzberg-Teller vibronic progressions in tip-position-resolved STML spectra, and we directly map out the vibronic coupling between the close-lying excited states of the molecules.

Institute of Physics Czech Academy of Sciences Cukrovarnická 10 16200 Prague Czech Republic

Université de Franche Comté CNRS FEMTO ST F 25000 Besançon France

Université de Strasbourg CNRS IPCMS UMR 7504 F 67000 Strasbourg France

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