Coinage metal nanostructures support localised surface plasmons, which confine optical fields much tighter than their wavelength (1). This extreme enhancement enables vibrational spectroscopy within small volumes, even down to single molecules (2,3). For many years lateral resolution was believed to be 10 nm (4), however recent experiments resolve the atomic structure of single molecules using tipenhanced Raman spectroscopy (3) and directly sequence RNA strands (5). Atomistic simulations also suggest plasmonic confinement to atomic scales is possible (6). Here we show that light-activated mobilisation of surface atoms in a plasmonic hotspot triggers the formation of additional 'picocavities'bounded by a single gold atom. Their ultra-small light localisation alters which vibrational modes of trapped molecules are observed, due to strong optical field gradients that switch the Raman selection rules. The resulting cascaded ultra-strong plasmonic confinement pumps specific molecular bonds, thereby creating non-thermal vibrational populations, and forms a new type of optomechanical

Unambiguous chemical identification of individual molecules closely packed on a surface can offer the possibility to address single chemical species and monitor their behaviour at the individual level. Such a degree of spatial resolution can in principle be achieved by detecting their vibrational fingerprints using tip-enhanced Raman scattering (TERS). The chemical specificity of TERS can be combined with the high spatial resolution of scanning probe microscopy techniques, an approach that has stimulated extensive research in the field. Recently, the development of nonlinear TERS in a scanning tunnelling microscope has pushed the spatial resolution down to ∼0.5 nm, allowing the identification of the vibrational fingerprints of isolated molecules on Raman-silent metal surfaces. Although the nonlinear TERS component is likely to help sharpen the optical contrast of the acquired image, the TERS signal still contains a considerable contribution from the linear term, which is spatially less confined. Therefore, in the presence of different adjacent molecules, a mixing of Raman signals may result. Here, we show that using a nonlinear scanning tunnelling microscope-controlled TERS set-up, two different adjacent molecules that are within van der Waals contact and of very similar chemical structure (a metal-centred porphyrin and a free-base porphyrin) on a silver surface can be distinguished in real space. In addition, with the help of density functional theory simulations, we are also able to determine their adsorption configurations and orientations on step edges and terraces.

The coherent interaction between quantum emitters and photonic modes in cavities underlies many of the current strategies aiming at generating and controlling photonic quantum states. A plasmonic nanocavity provides a powerful solution for reducing the effective mode volumes down to nanometre scale, but spatial control at the atomic scale of the coupling with a single molecular emitter is challenging. Here we demonstrate sub-nanometre spatial control over the coherent coupling between a single molecule and a plasmonic nanocavity in close proximity by monitoring the evolution of Fano lineshapes and photonic Lamb shifts in tunnelling electron-induced luminescence spectra. The evolution of the Fano dips allows the determination of the effective interaction distance of ∼1 nm, coupling strengths reaching ∼15 meV and a giant self-interaction induced photonic Lamb shift of up to ∼3 meV. These results open new pathways to control quantum interference and field–matter interaction at the nanoscale.

No abstract