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.

The optical properties of chromophores can be efficiently tuned by electrostatic fields generated in their close environment, a phenomenon that plays a central role for the optimization of complex functions within living organisms where it is known as internal Stark effect (ISE). Here, we realised an ISE experiment at the lowest possible scale, by monitoring the Stark shift generated by charges confined within a single chromophore on its emission energy. To this end, a scanning tunneling microscope (STM) functioning at cryogenic temperatures is used to sequentially remove the two central protons of a free-base phthalocyanine chromophore deposited on a NaCl-covered Ag(111) surface. STM-induced fluorescence measurements reveal spectral shifts that are associated to the electrostatic field generated by the internal charges remaining in the chromophores upon deprotonation.

Micro-ring resonators made of titanium dioxide were decorated with local light sources comprising CdSe/CdS colloidal quantum dot aggregates. The active micro-resonators are operated to achieve efficient evanescent excitation of nearby co-planar integrated waveguides. Coupled-mode analysis and numerical simulations are used to capture the dynamic of the optical interaction between locally activated resonators and integrated waveguides. In this context, we exemplify the key role of resonator intrinsic loss. Next, we show that locally activated or bus-waveguide excited resonators are in optimum waveguide interaction for the same so-called critical coupling condition, although the physical origin of this property is different for each configuration. More importantly, we found that a locally activated resonator is a fabrication imperfection tolerant configuration for the coupling light of local sources into waveguides. This remarkable property originates from the opposite change of the power cycling into the resonator and the waveguide coupling efficiency as a function of the resonator-waveguide separation gap. By operating an 8-μm-radius ring resonator with loaded quality factors around Q = 2100, we experimentally demonstrate a 5.5-dB enhancement of the power coupled into the output waveguide compared to a direct local source waveguide excitation.