The Single Molecule Probe: Nanoscale Vectorial Mapping of Photonic Mode Density in a Metal Nanocavity

We use superresolution single-molecule polarization and lifetime imaging to probe the local density of states (LDOS) in a metal nanocavity. Determination of the orientation of the molecular transition dipole allows us to retrieve the different LDOS behavior for parallel and perpendicular orientations with respect to the metal interfaces. For the perpendicular orientation, a strong lifetime reduction is observed for distances up to 150 nm from the cavity edge due to coupling to surface plasmon polariton modes in the metal. Contrarily, for the parallel orientation we observe lifetime variations resulting from coupling to characteristic λ/2 cavity modes. Our results are in good agreement with calculations of the nanoscale variations of the projected LDOS, which demonstrates the potential of single molecules as nonperturbative, nanoscale vectorial point probes in photonic and biological nanostructures.