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

Dielectric nanoparticles with moderately high refractive index and very low absorption (like Si and Ge in the visible−near-infrared (VIS−NIR) range) show a magnetodielectric behavior that produces interesting far-field coherent effects, like directionality phenomena or field enhancement in the proximity of the particle surface. As in the case of metals, ensembles of two or more dielectric particles can constitute basic elements for developing new spectroscopic tools based on surface field enhancement effects. Here we explore the electromagnetic behavior of the basic unit constituted by a dimer of dielectric nanoparticles made of moderately low-loss high refractive index material. The interactions responsible for the spectral features of the scattered radiation and field enhancement of the dimer are identified and studied through an analytical dipole−dipole model. The fluorescence of a single emitter (either electric or magnetic dipole) located in the dimer gap is also explored by calculating the quantum efficiencies and the quenching/enhancement of the radiation rates. Along this analysis, a comparison with metallic dimers is carried out. This study opens new possibilities to perform field-enhanced spectroscopy and sensing with nanostructures made of suitable dielectric materials.

Plasmon-enhanced Raman scattering can push single-molecule vibrational spectroscopy beyond a regime addressable by classical electrodynamics. We employ a quantum electrodynamics (QED) description of the coherent interaction of plasmons and molecular vibrations that reveal the emergence of nonlinearities in the inelastic response of the system. For realistic situations, we predict the onset of phonon-stimulated Raman scattering and a counterintuitive dependence of the anti-Stokes emission on the frequency of excitation. We further show that this QED framework opens a venue to analyze the correlations of photons emitted from a plasmonic cavity.Surface Enhanced Raman Scattering (SERS) is a spectroscopic technique in which the inelastic scattering from a molecule is increased by placing it in a hotspot of a plasmonic cavity, where the electric fields associated with the incident and the scattered photons are strongly enhanced (see the schematic in Fig. 1(a)). 1 The difference between the energy of those two photons provides a fingerprint of the molecule, i.e., detailed chemical information about its vibrational structure. Since the initial observation of Raman scattering from single molecules, 2,3 the use of a variety of plasmonic structures that act as effective optical nanoantennas over the last decades has allowed a tremendous advance of this molecular spectroscopy 4 . Metallic particles such as nanoshells 5,6 , nanorings 7 , nanorods 8 , nanowires 9 , or nano stars 10 , as well as plasmonic nanogap structures formed in particle dimers [11][12][13] , nanoparticle-on-a-mirror morphologies [14][15][16][17] , or nanoclusters 18 , are among the variety of structures that offer huge and controllable enhancements of the field intensity in their hotspots, boosting the inherently weak Raman scattering intensity, 1,19 and ultimately enabling the chemical identification and imaging of particular vibrational modes of a molecule with subnanometer resolution. 20 These results suggest that some experiments might have reached the regime where the quantum-mechanical nature of both the molecular vibrations and the plasmonic cavity emerges, 21 and call for an adequate theoretical description that goes beyond the classical treatment of the electric fields produced in plasmonic cavities. 1,22,23 In this work we address the underlying quantummechanical nature of Raman scattering processes by quantizing as bosonic excitations both the vibrations of the molecule and the electromagnetic field of a plasmonic cavity. The description of the vibrations through bosonic operators can be justified by considering the harmonic approximation to the energy landscape of the molecule along a generalized atomic coordinate ( Fig. 1(b)), such as the length of a molecular bond, e.g., C=O. 21,22 These vibrations interact with the cavity photons through a nonlinear Hamiltonian, reminiscent of that found in optomechanical systems. 24 In this description, the large enhancement of the Raman scattering from a molecule in the plasmonic cavity occurs thanks to ...

Plasmonic nanoparticles are commonly used to tune and direct the radiation from electric dipolar emitters. Less progress has been made towards understanding complementary systems of magnetic nature. However, it has been recently shown that high-index dielectric spheres can act as effective magnetic antennas. Here we explore the concept of coupling dielectric magnetic antennas with either an electric or magnetic dipolar emitter in a similar fashion to the purely electric systems reported previously. We investigate the enhancement of radiation from systems comprising admixtures of these electric and magnetic elements and perform a full study of its dependence on the distance and polarization of the emitter with respect to the antenna. A comparison to the plasmon antennas reveals remarkable symmetries between electric and magnetic systems, which might lead to novel paradigms in the design of nanophotonic devices that involve magnetic activity.