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The interactions between the excited states of a single chromophore withstatic and dynamic electric fields confined to a plasmonic cavity of picometerdimensions are investigated in a joint experimental and theoretical effort. Inthis configuration, the spatial extensions of the confined fields are smallerthan the one of the molecular exciton, a property that is used to generatefluorescence maps of the chromophores with intra-molecular resolution.Theoretical simulations of the electrostatic and electrodynamic interactionsoccurring at the chromophore-picocavity junction are able to reproduce andinterpret these hyper-resolved fluorescence maps, and reveal the key roleplayed by subtle variations of Purcell, Lamb and Stark effects at thechromophore-picocavity junction.

Mapping Lamb, Stark and Purcell effects at a chromophore-picocavity junction with hyper-resolved fluorescence microscopy