Role of metal-nanostructure features on tip-enhanced photoluminescence of single molecules

Tip-enhanced photoluminescence (TEPL) experiments have recently reached the ability to investigate single molecules exploiting resolution at the submolecular level. Localized surface plasmon resonances of metallic nanostructures have the capability of enhancing an impinging electromagnetic radiation in the proximity of their surface, with evident consequences both on absorption and emission of molecules placed in the same region. We propose a theoretical analysis of these phenomena in order to interpret TEPL experiments on single molecules, including a quantum mechanical description of the target molecule equilibrated with the presence of two nanostructures representative of the nanocavity usually employed in STMs. The approach has been applied to the zinc phthalocyanine molecule, previously considered in recent TEPL experiments [Yang et al., Nat. Photonics 14, 693-699 (2020)]. This work has the aim of providing a comprehensive theoretical understanding of the experimental results, particularly focusing on the investigation of the tip features that majorly influence the excitation and fluorescence processes of the molecule, such as the geometry, the dielectric function, and the tip-molecule distance.