Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy.

Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules and materials. However, probing how the electronics and dynamics of molecular systems change under strong coupling has been challenging due to the narrow range of spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational strong coupling (VSC) that are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC is shown to influence the equilibrium between two conformations of a molecular balance sensitive to London dispersion forces, revealing an apparent change in the equilibrium constant under VSC. In all compounds studied, VSC does not induce detectable changes in chemical shifts, J-couplings, or spin-lattice relaxation times. This unexpected finding indicates that VSC does not substantially affect molecular electron density distributions, and in turn has profound implications for the possible mechanisms at play in polaritonic chemistry under VSC and suggests that the emergence of collective behavior is critical.

Ensemble-Induced Strong Light-Matter Coupling of a Single Quantum Emitter.

We discuss a technique to strongly couple a single target quantum emitter to a cavity mode, which is enabled by virtual excitations of a nearby mesoscopic ensemble of emitters. A collective coupling of the latter to both the cavity and the target emitter induces strong photon nonlinearities in addition to polariton formation, in contrast to common schemes for ensemble strong coupling. We demonstrate that strong coupling at the level of a single emitter can be engineered via coherent and dissipative dipolar interactions with the ensemble, and provide realistic parameters for a possible implementation with SiV^{-} defects in diamond. Our scheme can find applications, amongst others, in quantum information processing or in the field of cavity-assisted quantum chemistry.

Tilting a ground-state reactivity landscape by vibrational strong coupling.

Many chemical methods have been developed to favor a particular product in transformations of compounds that have two or more reactive sites. We explored a different approach to site selectivity using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. Specifically, we studied the reactivity of a compound bearing two possible silyl bond cleavage sites-Si-C and Si-O, respectively-as a function of VSC of three distinct vibrational modes in the dark. The results show that VSC can indeed tilt the reactivity landscape to favor one product over the other. Thermodynamic parameters reveal the presence of a large activation barrier and substantial changes to the activation entropy, confirming the modified chemical landscape under strong coupling.

Conductivity in organic semiconductors hybridized with the vacuum field.

Much effort over the past decades has been focused on improving carrier mobility in organic thin-film transistors by optimizing the organization of the material or the device architecture. Here we take a different path to solving this problem, by injecting carriers into states that are hybridized to the vacuum electromagnetic field. To test this idea, organic semiconductors were strongly coupled to plasmonic modes to form coherent states that can extend over as many as 10(5) molecules and should thereby favour conductivity. Experiments show that indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility. A theoretical quantum model confirms the delocalization of the wavefunctions of the hybridized states and its effect on the conductivity. Our findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.

Coherent coupling of molecular resonators with a microcavity mode.

The optical hybridization of the electronic states in strongly coupled molecule-cavity systems have revealed unique properties, such as lasing, room temperature polariton condensation and the modification of excited electronic landscapes involved in molecular isomerization. Here we show that molecular vibrational modes of the electronic ground state can also be coherently coupled with a microcavity mode at room temperature, given the low vibrational thermal occupation factors associated with molecular vibrations, and the collective coupling of a large ensemble of molecules immersed within the cavity-mode volume. This enables the enhancement of the collective Rabi-exchange rate with respect to the single-oscillator coupling strength. The possibility of inducing large shifts in the vibrational frequency of selected molecular bonds should have immediate consequences for chemistry.

Sorting nanoparticles with intertwined plasmonic and thermo-hydrodynamical forces.

We exploit plasmonic and thermo-hydrodynamical forces to sort gold nanoparticles in a microfluidic environment. In the appropriate regime, the experimental data extracted from a Brownian statistical analysis of the kinetic motions are in good agreement with Mie-type theoretical evaluations of the optical forces acting on the nanoparticles in the plasmonic near field. This analysis enables us to demonstrate the importance of thermal and hydrodynamical effects in a sorting perspective.

Diffraction regimes of single holes.

We investigate both experimentally and theoretically the far-field diffraction patterns of single circular apertures as a function of their diameters d and at a given illumination wavelength λ. We observe the transition between the well-known pseudoscalar regime of large holes (d≫λ) and the less-known vectorial regime of subwavelength ones (d≪λ). Four different diffraction regimes are identified for different d/λ regions, each one with its polarization dependence. A thorough comparison with a theoretical model, which takes into account both finite hole size and the dielectric properties of the metal, allows us to explain and understand the physical processes leading to this behavior. Our results reveal the subtle interplay between two competing factors, one related to polarization symmetries associated with surface-plasmon excitations and the other originating in the coupling of the field to the waveguide mode of the aperture.

Weak measurements of light chirality with a plasmonic slit.

We examine, both experimentally and theoretically, an interaction of tightly focused polarized light with a slit on a metal surface supporting plasmon-polariton modes. Remarkably, this simple system can be highly sensitive to the polarization of the incident light and offers a perfect quantum weak measurement tool with a built-in postselection in the plasmon-polariton mode. We observe the plasmonic spin Hall effect in both coordinate and momentum spaces which is interpreted as weak measurements of the helicity of light with real and imaginary weak values determined by the input polarization. Our experiment combines the advantages of (i) quantum weak measurements, (ii) near-field plasmonic systems, and (iii) high-numerical aperture microscopy in employing the spin-orbit interaction of light and probing light chirality.

Brownian motion in a designer force field: dynamical effects of negative refraction on nanoparticles.

Photonic crystals (PC) have demonstrated unique features that have renewed the fields of classical and quantum optics. Although holding great promises, associated mechanical effects have proven challenging to observe. We demonstrate for the first time that one of the most salient properties of PC, namely negative refraction, can induce specific forces on metal nanoparticles. By integrating a periodically patterned metal film in a fluidic cell, we show that near-field optical forces associated with negatively refracted surface plasmons are capable of controlling particle trajectories. Coupling particle motions to PC band structures draws new approaches and strategies for parallel and high resolution all-optical control of particle flows with applications for micro- and nanofluidic systems.

Self-collimation of surface plasmon beams.

We generate self-collimating surface plasmon beams in a doubly periodic plasmonic grating. The self-collimation effect is understood from the local anisotropy of the isofrequency surface of the grating in the vicinity of the bandgap. The properties of the beams are analyzed by leakage radiation microscopy and show to an unprecedented level significantly reduced diffraction as compared with plasmon beams propagating on a flat metal film.

Plasmonic coherent drive of an optical trap.

We demonstrate that optical trapping can be driven by delocalized surface plasmon modes resonantly excited within a standing wave trap. Dynamical modifications are shown to be determined by the near-field symmetry of the plasmonic modes with negligible thermal effect. With low trapping powers and polarization control, remarkable stiffness enhancements are recorded, the larger the smaller the particle. The results can be simply modeled accounting for a coherent interaction between the plasmon field and the Gaussian standing wave of the trap.

Mechanisms for extraordinary optical transmission through bull's eye structures.

We analyze both experimentally and theoretically the physical mechanisms that determine the optical transmission through deep sub-wavelength bull's eye structures (concentric annular grooves surrounding a circular hole). Our analysis focus on the transmission resonance as a function of the distance between the central hole and its nearest groove. We find that, for that resonance, each groove behaves almost independently, acting as an optical cavity that couples to incident radiation, and reflecting the surface plasmons radiated by the other side of the same cavity. It is the constructive contribution at the central hole of these standing waves emitted by independent grooves which ends up enhancing transmission. Also for each groove the coupling and reflection coefficients for surface plasmons are incorporated into a phenomenological Huygens-Fresnel model that gathers the main mechanisms to enhance transmission. Additionally, it is shown that the system presents a collective resonance in the electric field that does not lead to resonant transmission, because the fields radiated by the grooves do not interfere constructively at the central hole.

Reversible switching of ultrastrong light-molecule coupling.

We demonstrate that photochromic molecules enable switching from the weak- to ultrastrong-coupling regime reversibly, by using all-optical control. This switch is achieved by photochemically inducing conformational changes in the molecule. Remarkably, a Rabi splitting of 700 meV is measured at room temperature, corresponding to 32% of the molecular transition energy. A similar coupling strength is demonstrated in a plasmonic structure. Such systems present a unique combination of coupling strength and functional capacities.

Surface plasmon leakage radiation microscopy at the diffraction limit.

This paper describes the image formation process in optical leakage radiation microscopy of surface plasmon-polaritons with diffraction limited spatial resolution. The comparison of experimentally recorded images with simulations of point-like surface plasmon-polariton emitters allows for an assignment of the observed fringe patterns. A simple formula for the prediction of the fringe periodicity is presented and practically relevant effects of abberations in the imaging system are discussed.

Optimization of bull's eye structures for transmission enhancement.

We present an exhaustive exploration of the parameter space defining the optical properties of a bull's eye structure, both experimentally and theoretically. By studying the resonance intensity variations associated with the different geometrical features, several parameters are seen to be interlinked and scale laws emerge. From the results it is possible to give a simple recipe to design a bull's eye structure with optimal transmission properties.

Enhanced optical transmission at the cutoff transition.

The phenomenon of extraordinary transmission in the optical regime for circular hole arrays in optically thick metal films is studied as a function of hole size and depth. In the limit of small holes compared to the depth, the transmission properties follow a waveguide type behavior. By describing the transmission process as resulting from the interference between a resonant and a non-resonant contribution, a transition is clearly revealed through the specific spectral variations of the resonance at a given hole depth. This transition is associated to a change in the attenuation through the hole as its size increases, and corresponds to the optimal condition for surface plasmon excitation.

Light in tiny holes.

The presence of tiny holes in an opaque metal film, with sizes smaller than the wavelength of incident light, leads to a wide variety of unexpected optical properties such as strongly enhanced transmission of light through the holes and wavelength filtering. These intriguing effects are now known to be due to the interaction of the light with electronic resonances in the surface of the metal film, and they can be controlled by adjusting the size and geometry of the holes. This knowledge is opening up exciting new opportunities in applications ranging from subwavelength optics and optoelectronics to chemical sensing and biophysics.

Optimization of surface plasmons launching from subwavelength hole arrays: modelling and experiments.

The launching of surface plasmons by micro-gratings of subwavelength apertures milled in a thick metal film is important for the development of surface plasmon based circuits. By comparing the near-field optical images of such surface plasmon sources with the results of a Huygens-Fresnel principle based scattering model, we show that the properties of the locally launched SP beams such as divergence or uniformity can be tuned by adjusting the shape of the micro-gratings. This allows us to propose an optimized source array well adapted for providing a narrow, collimated and uniform beam.

Surface plasmon polaritons and their role in the enhanced transmission of light through periodic arrays of subwavelength holes in a metal film.

We present results of the transmitted, reflected, and absorbed power associated with the enhanced transmittance of light through a silver film pierced by a periodic array of subwavelength holes. Comparing experimentally acquired dispersion curves under different polarization conditions shows that the transmission features of the array are consistent with p-polarized resonant modes of the structure. By exploring the regime in which no propagating diffracted orders are allowed, we further show that the transmittance maxima are associated with both reflectance minima and absorption maxima. These new results provide strong experimental evidence for transmission based on diffraction, assisted by the enhanced fields associated with surface plasmon polaritons.

Multiple paths to enhance optical transmission through a single subwavelength slit.

In this Letter, we explore transmission properties of a single subwavelength slit flanked by a finite array of grooves made on a thick metallic film. We identify three main mechanisms that can enhance optical transmission: groove cavity mode excitation (controlled by the depth of the grooves), in-phase groove reemission (controlled by the period of the groove array), and slit waveguide mode (controlled by the thickness of the metal film). By tuning these geometrical parameters, enhancements of transmission of light by up to 2 orders of magnitude can be achieved when all three mechanisms coincide. Experimental verification of these findings is also shown for structured silver films fabricated by focused-ion-beam milling.