In a research article published last year we reported red shifting of the charge transfer band of Reichardt’s dye in the visible spectrum when the solvent was vibrationally coupled to an optical cavity, indicating a change in the polarity of the solvent. The magnitude of the observed shifts correlated with the alkyl chain length of the alcohol solvents and with their polarizability and solvent-accessible surface area. Control experiments under off-resonance conditions in which none of the vibrational bands of interest were coupled to the cavity showed no shifts. We interpreted these experiments as evidence that strong coupling is responsible for the observed shifting, and that the change in solvent polarity was due to the impact of vibrational strong coupling (VSC) on London dispersion forces within the coupled solvent. However, additional experiments and transfer matrix simulations (TMS) to mimic the transmission of light through the optical Fabry Perot (FP) cavity have caused us to revisit this interpretation. We now believe that the observed shifts for Reichardt’s dye were an optical artifact caused by neglecting reflection when measuring absorbance in transmission mode. Unfortunately, the parameters found to modulate the magnitude of the shift in our experiments were also found to do the same in the TMS. We regret to not have identified the underlying reason for the shift in the absorption spectrum and hope that the simulation results presented here will be instructive for the Strong Coupling community. This spectral error does not undermine the conclusion of other published studies showing effects of VSC on London dispersion forces.

Light-matter interactions have generated considerable interest as a means to manipulate material properties. Light-induced superconductivity has been demonstrated using pulsed lasers. An attractive alternative possibility is to exploit strong light-matter interactions arising by coupling phonons to the vacuum electromagnetic field of a cavity mode as has been suggested and theoretically studied. Here we explore this possibility for two very different superconductors, namely YBCO (YBa$_2$Cu$_3$O$_{6+x}$) and Rb$_3$C$_{60}$, coupled to surface plasmon polaritons, using a novel cooperative effect based on the presence of a strongly coupled vibrational environment allowing efficient dressing of the otherwise weakly coupled phonon bands of these compounds. By placing the superconductor-surface plasmon system in a SQUID magnetometer, we find that the superconducting transition temperatures ($T_{c}$) for both compounds are modified in the absence of any external laser field. For YBCO, $T_{c}$ decreases from 92 K to 86 K while for Rb$_3$C$_{60}$, it increases from 30 K to 45 K at normal pressures. In the latter case, a simple theoretical framework is provided to understand these results based on an enhancement of the electron-phonon coupling. This proof-of-principle study opens a new tool box to not only modify superconducting materials but also to understand the mechanistic details of different superconductors.

Optically activated reactions initiate biological processes such as photosynthesis or vision, but can also control polymerization, catalysis or energy conversion. Methods relying on the manipulation of light at macroscopic and mesoscopic scales are used to control on-surface photochemistry, but do not offer atomic-scale control. Here we take advantage of the confinement of the electromagnetic field at the apex of a scanning tunnelling microscope tip to drive the phototautomerization of a free-base phthalocyanine with submolecular precision. We can control the reaction rate and the relative tautomer population through a change in the laser excitation wavelength or through the tip position. Atomically resolved tip-enhanced photoluminescence spectroscopy and hyperspectral mapping unravel an excited-state mediated process, which is quantitatively supported by a comprehensive theoretical model combining ab initio calculations with a parametric open-quantum-system approach. Our experimental strategy may allow insights in other photochemical reactions and proof useful to control complex on-surface reactions. Weak laser light confined at the apex of a scanning tunnelling microscope tip can drive the tautomerization of a free-base phthalocyanine with atomic-scale precision. The combination of tip-enhanced photoluminescence spectroscopy and hyperspectral mapping paired with theoretical modelling then unravel an excited-state mediated reaction.

Vibrational strong coupling (VSC) occurs when molecular vibrations hybridize with the modes of an optical cavity, an interaction mediated by vacuum fluctuations. VSC has been shown to influence the rates and selectivity of chemical reactions. However, a clear understanding of the mechanism at play remains elusive. Here, we show that VSC affects the polarity of solvents, which is a parameter well-known to influence reactivity. The strong solvatochromic response of Reichardt's dye (RD) was used to quantify the polarity of a series of alcohol solvents at visible wavelengths. We observed that, by simultaneously coupling the OH and CH vibrational bands of the alcohols, the absorption maximum of Reichardt's dye redshifted by up to ∼15.1 nm, corresponding to an energy change of 5.1 kJ·mol-1. With aliphatic alcohols, the magnitude of the absorption change of RD was observed to be related to the length of the alkyl chain, the molecular surface area, and the polarizability, indicating that dispersion forces are impacted by strong coupling. Therefore, we propose that dispersion interactions, which themselves originate from vacuum fluctuations, are impacted under strong coupling and are therefore critical to understanding how VSC influences chemistry.

The scattering properties of metallic optical antennas are typically examined through the lens of their plasmonic resonances. However, non-plasmonic transition metals also sustain surface waves in the visible. We experimentally investigate in this work the far-field diffraction properties of apertured optical antennas milled on non-plasmonic W films and compare the results with plasmonic references in Ag and Au. The polarization-dependent diffraction patterns and the leakage signal emerging from apertured antennas in both kinds of metals are recorded and analyzed. This thorough comparison with surface plasmon waves reveals that surface waves are launched on W and that they have the common abilities to confine the visible light at metal-dielectric interfaces offering the possibility to tailor the far-field emission. The results have been analyzed through theoretical models accounting for the propagation of a long range surface mode launched by subwavelength apertures, that is scattered in free space by the antenna. This surface mode on W can be qualitatively described as an analogy in the visible of the Zenneck wave in the radio regime. The nature of the new surface waves have been elucidated from a careful analysis of the asymptotic expansion of the electromagnetic propagators, which provides a convenient representation for explaining the Zenneck-like character of the excited waves and opens new ways to fundamental studies of surface waves at the nanoscale beyond plasmonics.

Ultrafast manipulation of light polarization is crucial in many nonlinear optic and optoelectronic operations. However, most of the configurations are suffering from low modulation speed (gigahertz) or small contrast ratio. Here, by taking advantange of the anisotropic nonlinear response of indium tin oxide at its epsilon-near-zero region and plasmonic nanoantennas at their polarization-sensitive resonance, we achieve a large, ultrafast anisotropic modulation of light. A polarization elliptic rotation of 32.5 degrees at 1.23 mu m wavelength, and a phase delay between the oscillations of the linear polarization axes of pi/7 within 600 fs response time is demonstrated. This approach constitutes a novel, efficient way to implement all-optical high-speed polarization modulators and retarders.

Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid-rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry-Perot cavity. Absorption and fluorescence studies indicate a large modification of the self-assembly under such cooperative VSC. Electron microscopy confirms that in this case, the supramolecular morphology is totally different from that observed in the absence of strong coupling. In addition, the self-assembly kinetics are altered and depend on the solvent vibration under VSC. The results are compared to kinetic isotope effects on the self-assembly to help clarify the role of different parameters under strong coupling. These findings indicate that VSC is a valuable new tool for controlling supramolecular assemblies with broad implications for the molecular and material sciences.

The combination of surface-enhanced resonance Raman spectroscopy (SERRS) and electrochemistry is an ideal tool to study the redox process of the heme proteins and is often performed on silver electrodes. In this manuscript, we present an approach using a microstructured gold surface that serves as the electrochemical working electrode, and at the same time, acts as SERS active substrate. The cell requires a micromolar concentration of sample at the electrode surface. Even if the performance of the gold grid as SERS substrate exhibited a smaller enhancement factor than expected for silver, oxidized and reduced spectra of proteins (Сyt c, Hb and Mb) monolayers could be obtained and the characteristic redox dependent shifts of the marker bands ν19, ν4 and ν10 were seen. The easy modification protocol and the higher stability of the gold electrode towards oxidative currents are the advantages of the present spectroeletrochemical cell. Finally, FDTD simulations confirm that the roughness of the gold grid has an effect on the Raman enhancement of the adsorbed proteins.

Vibrational strong coupling (VSC) is currently emerging as a tool to control chemical dynamics. Here we study the impact of strong coupling strength, given by the Rabi splitting energy (ħΩR), on the thermodynamic parameters associated with the transition state of the desilylation reaction of the model molecule 1-phenyl-2-trimethylsilylacetylene. Under VSC, the enthalpy and entropy of activation determined from the temperature-dependent kinetic studies varied nonlinearly with the coupling strength. The thermodynamic parameters of the noncavity reaction did not show noticeable variation, ruling out concentration effects other than the enhanced ħΩR for the changes observed under VSC. The difference between the total free energy change under VSC and in noncavity was relatively smaller possibly because the enthalpy and entropy of activation compensate each other. This thermodynamic study gives more insight into the role of collective strong coupling on the transition state that leads to modified dynamics and branching ratios.

It has been shown that light-matter strong coupling of materials can lead to modified and often improved properties which has stimulated considerable interest. While charge transport can be enhanced in n-type organic semiconductors by coupling the electronic transition and thereby splitting the conduction band into polaritonic states, it is not clear whether the same process can also influence carrier transport in the valence band of p-type semiconductors. Here we demonstrate for the first time that it is indeed possible to enhance both the conductivity and photoconductivity of a p-type semiconductor rr-P3HT that is ultra-strongly coupled to plasmonic modes. It is due to the hybrid light-matter character of the virtual polaritonic excitations affecting the linear-response of the material. Furthermore, in addition to being enhanced, the photoconductivity of rr-P3HT shows modified spectral response due to the formation of the hybrid polaritonic states. This illustrates the potential of engineering the vacuum electromagnetic environment to improve the opto-electronic properties of organic materials.

Vibrational strong coupling (VSC) has recently emerged as a completely new tool for influencing chemical reactivity. It harnesses electromagnetic vacuum fluctuations through the creation of hybrid states of light and matter, called polaritonic states, in an optical cavity resonant to a molecular absorption band. Here, we investigate the effect of vibrational strong coupling of water on the enzymatic activity of pepsin, where a water molecule is directly involved in the enzyme's chemical mechanism. We observe an approximately 4.5-fold decrease of the apparent second-order rate constant kcat /Km when coupling the water stretching vibration, whereas no effect was detected for the strong coupling of the bending vibration. The possibility of modifying enzymatic activity by coupling water demonstrates the potential of VSC as a new tool to study biochemical reactivity.

The strong coupling regime of light–matter interaction has recently been extended to IR active molecular vibrations coupled to microcavities, resulting in the formation of so-called vibro-polaritonic states. Here we demonstrate the emissivity of such hybrid states. Using thermal excitation, we achieve polaritonic IR emission from a strongly coupled polymer. Thermal excitation of vibro-polaritons, thus, constitutes an original way of establishing sizable excited-states populations in strongly coupled systems and opens new routes to the study of interacting vibro-polaritons.

The predominance of interface resistance makes current crowding ubiquitous in short channel organic electronics devices but its impact on spin transport has never been considered. We investigate electrochemically doped nanoscale PBTTT short channel devices and observe the smallest reported values of crowding lengths, found for sub-100 nm electrodes separation. These observed values are nevertheless exceeding the spin diffusion lengths reported in the literature. We discuss here how current crowding can be taken into account in the framework of the Fert-Jaffrès model of spin current propagation in heterostructures, and predict that the anticipated resulting values of magnetoresistance can be significantly reduced. Current crowding therefore impacts spin transport applications and interpretation of the results on spin valve devices.

Quantum plasmonics lies at the intersection between nanophotonics and quantum optics. Genuine quantum effects can be observed with non-classical states such as Fock states and with entangled states. A N00N state combines both aspects: it is a quantum superposition state of a Fock state with N excitations in two spatial modes. Here we report the first observation of two-plasmon (N = 2) N00N state interferences using a plasmonic beamsplitter etched on a planar interface between gold and air. We analyze in detail the role of losses at the beamsplitter and during the propagation along the metal/air interface. While the intrinsic losses of the beamsplitter are responsible for the emergence of quantum nonlinear absorption, we note that N00N states decay N times faster than classical states due to propagation losses.

The growing field of quantum plasmonics lies at the intersection between nanophotonics and quantum optics. QUantum plasmonics investigate the quantum properties of single surface plasmons, trying to reproduce fundamental and landmark quantum optics experiment that would benefit from the light-confinement properties of nanophotonic systems, thus paving the way towards the design of basic components dedicated to quantum experiments with sizes inferior to the diffraction limit. Several groups have recently reproduced fundamental quantum optics experiments with single surface plasmons polaritons (SPPs). We have investigated two situations of quantum interference of single SPPs on lossy beamsplitters : a plasmonic version of the Hong-Ou-Mandel experiment, and the observation of plasmonic N00N states interferences. We numerically designed and fabricated several beamsplitters that reveal new quantum interference scenarios, such as the coalescence and the anti-coalescence of SPPs, or quantum non-linear absorption. Our work show that losses can be seen as a new degree of freedom in the design of plasmonic devices.

Electronic light-matter strong coupling has been limited to solid molecular films due to the challenge of preparing optical cavities with nanoscale dimensions. Here we report a technique to fabricate such Fabry-Perot nanocavities in which solutions can be introduced such that light molecule interactions can be studied at will in the liquid phase. We illustrate the versatility of these cavities by studying the emission properties of Chlorin e6 solutions in both the weak and strong coupling regimes as a function of cavity detuning. Liquid nanocavities will broaden the investigation of strong coupling to many solution-based molecular processes.

In this experiment, pairs of identical photons at 806 nm through a single-photon down conversion in a nonlinear crystal that are sent onto a plasmonic platform were generated. The plasmonic platform consists in several elements that are etched on a 300 nm-thick gold film on top of a silica substrate, on a total 40x40μm footprint. The input channels of the plasmonic platform are made of two unidirectional launchers. Those asymmetric 11-grooves gratings have been designed to efficiently couple a normally incident Gaussian mode into directional SPPs. The SPPs generated by each launcher then freely propagate and recombine on the surface plasmon beamsplitter (SPBS). It is made of two identical grooves in the metallic surface, oriented at 45° with respect to the propagation direction of waves. The succession of metal and air allows a scattering process that generates both a transmitted and a reflected SPP. The SPPs then propagate towards two large outcoupling strip slits. They are decoupled into photons propagating in the glass substrate on the rear of the platform.

Two-boson interference, a fundamentally quantum effect, has been extensively studied with photons through the Hong-Ou-Mandel effect and observed with guided plasmons. Using two freely propagating surface plasmon polaritons (SPPs) interfering on a lossy beam splitter, we show that the presence of loss enables us to modify the reflection and transmission factors of the beam splitter, thus revealing quantum interference paths that do not exist in a lossless configuration. We investigate the two-plasmon interference on beam splitters with different sets of reflection and transmission factors. Through coincidence-detection measurements, we observe either coalescence or anti-coalescence of SPPs. The results show that losses can be viewed as a degree of freedom to control quantum processes.