Superlocalization Surface-Enhanced Raman Scattering Microscopy: Comparing Point Spread Function Models in the Ensemble and Single-Molecule Limits

Abstract

In this report, we compare the effectiveness of various dipole and Gaussian point spread function (PSF) models for fitting diffraction-limited surface-enhanced Raman scattering (SERS) emission images from rhodamine 6G-labeled nanoparticle dimers at both the high-concentration and single-molecule limit. Of all models tested, a 3-axis dipole PSF gives the best approximation to the experimental PSF, although none of the models utilized in the study were without systematic error when fitting the experimental data. In the high-concentration regime, all models localize the SERS emission to a stationary centroid position, with the dipole models providing additional orientation parameters that closely match the geometry of the dimer, indicating that the molecules are coupled to all resonant plasmon modes of the nanostructure. In the single-molecule case, the different models show a mobile SERS centroid, consistent with single-molecule motion on the surface, but the behavior of the centroid is model-dependent. Despite the centroid mobility in the single-molecule regime, the dipole PSF models still give accurate orientation information on the underlying dimer structure, although with less precision than the ensemble-averaged samples.