Locating Single-Atom Optical Picocavities Using Wavelength-Multiplexed Raman Scattering

[Image: see text] Transient atomic protrusions in plasmonic nanocavities confine optical fields to sub-1-nm(3) picocavities, allowing the optical interrogation of single molecules at room temperature. While picocavity formation is linked to both the local chemical environment and optical irradiation, the role of light in localizing the picocavity formation is unclear. Here, we combine information from thousands of picocavity events and simultaneously compare the transient Raman scattering arising from two incident pump wavelengths. Full analysis of the data set suggests that light suppresses the local effective barrier height for adatom formation and that the initial barrier height is decreased by reduced atomic coordination numbers near facet edges. Modeling the system also resolves the frequency-dependent picocavity field enhancements supported by these atomic scale features.