Strong coupling in molecular systems: a simple predictor employing routine optical measurements.

We provide a simple method that enables readily acquired experimental data to be used to predict whether or not a candidate molecular material may exhibit strong coupling. Specifically, we explore the relationship between the hybrid molecular/photonic (polaritonic) states and the bulk optical response of the molecular material. For a given material, this approach enables a prediction of the maximum extent of strong coupling (vacuum Rabi splitting), irrespective of the nature of the confined light field. We provide formulae for the upper limit of the splitting in terms of the molar absorption coefficient, the attenuation coefficient, the extinction coefficient (imaginary part of the refractive index) and the absorbance. To illustrate this approach, we provide a number of examples, and we also discuss some of the limitations of our approach.

Strong coupling-induced frequency shifts of highly detuned photonic modes in multimode cavities.

Strong coupling between light and molecules is a fascinating topic exploring the implications of the hybridization of photonic and molecular states. For example, many recent experiments have explored the possibility that strong coupling of photonic and vibrational modes might modify chemical reaction rates. In these experiments, reactants are introduced into a planar cavity, and the vibrational mode of a chemical bond strongly couples to one of the many photonic modes supported by the cavity. Some experiments quantify reaction rates by tracking the spectral shift of higher-order cavity modes that are highly detuned from the vibrational mode of the reactant. Here, we show that the spectral position of these cavity modes, even though they are highly detuned, can still be influenced by strong coupling. We highlight the need to consider this strong coupling-induced frequency shift of cavity modes if one is to avoid underestimating cavity-induced reaction rate changes. We anticipate that our work will assist in the re-analysis of several high-profile results and has implications for the design of future strong coupling experiments.

Selection Bias in Strong Coupling Experiments.

The strong coupling of light and molecules offers a potential new pathway to modify the properties of photonic modes and molecules. There are many reasons to be optimistic about the prospects of strong coupling; however, progress in this field is currently hindered by challenges in reproducibility, problems associated with differentiating between strong coupling and other effects, and the lack of a clear theoretical model to describe the reported effects. Concerning the question of differentiating between strong coupling and other possible mechanisms when examining experimental data, here, we show how cognitive bias can lead us to place undue emphasis on a given interpretation of unsystematic experimental data. We hope that this Viewpoint will, where appropriate, help readers to plan strong coupling experiments more carefully and evaluate the significance of the data obtained from them.

Non-Polaritonic Effects in Cavity-Modified Photochemistry.

Strong coupling of molecules to vacuum fields is widely reported to lead to modified chemical properties such as reaction rates. However, some recent attempts to reproduce infrared strong coupling results have not been successful, suggesting that factors other than strong coupling may sometimes be involved. In the first vacuum-modified chemistry experiment, changes to a molecular photoisomerization process in the ultraviolet-visible spectral range are attributed to strong coupling of the molecules to visible light. Here, this process is re-examined, finding significant variations in photoisomerization rates consistent with the original work. However, there is no evidence that these changes need to be attributed to strong coupling. Instead, it is suggested that the photoisomerization rates involved are most strongly influenced by the absorption of ultraviolet radiation in the cavity. These results indicate that care must be taken to rule out non-polaritonic effects before invoking strong coupling to explain any changes of properties arising in cavity-based experiments.

Raman Probing the Local Ultrastrong Coupling of Vibrational Plasmon Polaritons on Metallic Gratings.

Strong coupling of molecular vibrations with light creates polariton states, enabling control over many optical and chemical properties. However, the near-field signatures of strong coupling are difficult to map as most cavities are closed systems. Surface-enhanced Raman microscopy of open metallic gratings under vibrational strong coupling enables the observation of spatial polariton localization in the grating near field, without the need for scanning probe microscopies. The lower polariton is localized at the grating slots, displays a strongly asymmetric line shape, and gives greater plasmon-vibration coupling strength than measured in the far field. Within these slots, the local field strength pushes the system into the ultrastrong coupling regime. Models of strong coupling which explicitly include the spatial distribution of emitters can account for these effects. Such gratings enable exploration of the rich physics of polaritons, its impact on polariton chemistry under flow conditions, and the interplay between near- and far-field properties through vibrational polariton-enhanced Raman scattering.

Origin of an Anticrossing between a Leaky Photonic Mode and an Epsilon-Near-Zero Point of Silver.

Strong light-matter coupling hybridizes light and matter to form states known as polaritons, which give rise to a characteristic anticrossing signature in dispersion plots. Here, we identify conditions under which an anticrossing can occur in the absence of strong coupling. We study planar silver/dielectric structures and find that, around the epsilon-near-zero point in silver, the impedance matching between the silver and dielectric layers gives rise to an anticrossing. Our work shows that care must be taken to ensure that anticrossing arising from impedance matching is not misattributed to strong coupling.

Theory of strong coupling between molecules and surface plasmons on a grating.

The strong coupling of molecules with surface plasmons results in hybrid states which are part molecule, part surface-bound light. Since molecular resonances may acquire the spatial coherence of plasmons, which have mm-scale propagation lengths, strong-coupling with molecular resonances potentially enables long-range molecular energy transfer. Gratings are often used to couple incident light to surface plasmons, by scattering the otherwise non-radiative surface plasmon inside the light-line. We calculate the dispersion relation for surface plasmons strongly coupled to molecular resonances when grating scattering is involved. By treating the molecules as independent oscillators rather than the more typically considered single collective dipole, we find the full multi-band dispersion relation. This approach offers a natural way to include the dark states in the dispersion. We demonstrate that for a molecular resonance tuned near the crossing point of forward and backward grating-scattered plasmon modes, the interaction between plasmons and molecules gives a five-band dispersion relation, including a bright state not captured in calculations using a single collective dipole. We also show that the role of the grating in breaking the translational invariance of the system appears in the position-dependent coupling between the molecules and the surface plasmon. The presence of the grating is thus not only important for the experimental observation of molecule-surface-plasmon coupling, but also provides an additional design parameter that tunes the system.

Role of Symmetry Breaking in Observing Strong Molecule-Cavity Coupling Using Dielectric Microspheres.

The emergence of dielectric open optical cavities has opened a new research avenue in nanophotonics. In particular, dielectric microspheres support a rich set of cavity modes with varying spectral characteristics, making them an ideal platform to study molecule-cavity interactions. The symmetry of the structure plays a critical role in the outcoupling of these modes and, hence, the perceived molecule-cavity coupling strength. Here, we experimentally and theoretically study molecule-cavity coupling mediated by the Mie scattering modes of a dielectric microsphere placed on a glass substrate and excited with far-field illumination, from which we collect scattering signatures both in the air and glass sides. Glass-side collection reveals clear signatures of strong molecule-cavity coupling (coupling strength 2g = 74 meV), in contrast to the air-side scattering signal. Rigorous electromagnetic modeling allows us to understand molecule-cavity coupling and unravel the role played by the spatial mode profile in the observed coupling strength.

All-optical control of phase singularities using strong light-matter coupling.

Strong light-matter coupling occurs when the rate of energy exchange between an electromagnetic mode and a molecular ensemble exceeds competing dissipative processes. The study of strong coupling has been motivated by applications such as lasing and the modification of chemical processes. Here we show that strong coupling can be used to create phase singularities. Many nanophotonic structures have been designed to generate phase singularities for use in sensing and optoelectronics. We utilise the concept of cavity-free strong coupling, where electromagnetic modes sustained by a material are strong enough to strongly couple to the material's own molecular resonance, to create phase singularities in a simple thin film of organic molecules. We show that the use of photochromic molecules allows for all-optical control of phase singularities. Our results suggest what we believe to be both a new application for strong light-matter coupling and a new, simplified, more versatile means of manipulating phase singularities.

Implicit image processing with ghost imaging.

In computational ghost imaging, the object is illuminated with a sequence of known patterns and the scattered light is collected using a detector that has no spatial resolution. Using those patterns and the total intensity measurement from the detector, one can reconstruct the desired image. Here we study how the reconstructed image is modified if the patterns used for the illumination are not the same as the reconstruction patterns and show that one can choose how to illuminate the object, such that the reconstruction process behaves like a spatial filtering operation on the image. The ability to directly measure a processed image allows one to bypass the post-processing steps and thus avoid any noise amplification they imply. As a simple example we show the case of an edge-detection filter.

Strong Coupling of Multimolecular Species to Soft Microcavities.

Can we couple multiple molecular species to soft cavities? The answer to this question has relevance in designing open cavities for polaritonic chemistry applications. Because of the differences in adhesiveness, it is difficult to couple multiple molecular species to open cavities in a controlled and precise manner. In this Letter, we discuss the procedure to coat multiple dyes, TDBC and S2275, onto a dielectric microsphere using a layer-by-layer deposition technique so as to facilitate the multimolecule coupling. We observed the formation of a middle polariton branch due to the intermolecular mixing facilitated by the whispering gallery modes. The coupling strength, 2g, of the TDBC molecules was found to be 98 meV, while that of the S2275 molecules was 78 meV. The coupling strength was found to be greater than the cavity line width and the molecular absorption line width, showing that the system is in the strong coupling regime.

Metamaterial Analogues of Strongly Coupled Molecular Ensembles.

The formation of polariton modes due to the strong coupling of light and matter has led to exciting developments in physics, chemistry, and materials science. The potential to modify the properties of molecular materials by strongly coupling molecules to a confined light field is so far-reaching and so attractive that a new field known as "polaritonic chemistry" is now emerging. However, the molecular scale of the materials involved makes probing strong coupling at the individual resonator level extremely challenging. Here, we offer a complementary approach based upon metamaterials, an approach that enables us to use cm-scale structures, thereby opening a new way to explore strong coupling phenomena. As proof-of-principle, we show that metamolecules placed inside a radio frequency cavity may exhibit strong coupling and show that near-field radio frequency techniques allow us, for the first time, to probe the response of individual metamolecules under strong coupling conditions.

Polariton assisted photoemission from a layered molecular material: role of vibrational states and molecular absorption.

The way molecules absorb, transfer, and emit light can be modified by coupling them to optical cavities. The extent of the modification is often defined by the cavity-molecule coupling strength, which depends on the number of coupled molecules. We experimentally and numerically study the evolution of photoemission from a thin layered J-aggregated molecular material strongly coupled to a Fabry-Perot microcavity as a function of the number of coupled layers. We unveil an important difference between the strong coupling signatures obtained from reflection spectroscopy and from polariton assisted photoluminescence. We also study the effect of the vibrational modes supported by the molecular material on the polariton assisted emission both for a focused laser beam and for normally incident excitation, for two different excitation wavelengths: a laser in resonance with the lower polariton branch, and a laser not in resonance. We found that Raman scattered photons appear to play an important role in populating the lower polariton branch, especially when the system was excited with a laser in resonance with the lower polariton branch. We also found that the polariton assisted photoemission depends on the extent of modification of the molecular absorption induced by the molecule-cavity coupling.

Cavity-Free Ultrastrong Light-Matter Coupling.

Strong coupling between light and matter can occur when the interaction strength between a confined electromagnetic field and a molecular resonance exceeds the losses to the environment, leading to the formation of hybrid light-matter states known as polaritons. Ultrastrong coupling occurs when the coupling strength becomes comparable to the transition energy of the system. It is widely assumed that the confined electromagnetic fields necessary for strong coupling to organic molecules can only be achieved with external structures such as Fabry-Pérot resonators, plasmonic nanostructures, or dielectric resonators. Here we show experimentally that such structures are unnecessary and that a simple dielectric film of dye molecules supports sufficiently modified vacuum electromagnetic fields to enable room-temperature ultrastrong light-matter coupling. Our results may be of use in the design of experiments to probe polaritonic chemistry and suggest that polaritonic states are perhaps easier to realize than previously thought.

All-optical switching of an epsilon-near-zero plasmon resonance in indium tin oxide.

Nonlinear optical devices and their implementation into modern nanophotonic architectures are constrained by their usually moderate nonlinear response. Recently, epsilon-near-zero (ENZ) materials have been found to have a strong optical nonlinearity, which can be enhanced through the use of cavities or nano-structuring. Here, we study the pump dependent properties of the plasmon resonance in the ENZ region in a thin layer of indium tin oxide (ITO). Exciting this mode using the Kretschmann-Raether configuration, we study reflection switching properties of a 60 nm layer close to the resonant plasmon frequency. We demonstrate a thermal switching mechanism, which results in a shift in the plasmon resonance frequency of 20 THz for a TM pump intensity of 70 GW cm-2. For degenerate pump and probe frequencies, we highlight an additional two-beam coupling contribution, not previously isolated in ENZ nonlinear optics studies, which leads to an overall pump induced change in reflection from 1% to 45%.

Single vs double anti-crossing in the strong coupling between surface plasmons and molecular excitons.

Strong coupling between surface plasmons and molecular excitons may lead to the formation of new hybrid states-polaritons-that are part light and part matter in character. A key signature of this strong coupling is an anti-crossing of the exciton and surface plasmon modes on a dispersion diagram. In a recent report on strong coupling between the plasmon modes of a small silver nano-rod and a molecular dye, it was shown that when the oscillator strength of the exciton is large enough, an additional anti-crossing feature may arise in the spectral region where the real part of the permittivity of the excitonic material is zero. However, the physics behind this double anti-crossing feature is still unclear. Here, we make use of extensive transfer matrix simulations to explore this phenomenon. We show that for low oscillator strengths of the excitonic resonance, there is a single anti-crossing arising from strong coupling between the surface plasmon and the excitonic resonance, which is associated with the formation of upper and lower plasmon-exciton polaritons. As the oscillator strength is increased, we find that a new mode emerges between these upper and lower polariton states and show that this new mode is an excitonic surface mode. Our study also features an exploration of the role played by the orientation of the excitonic dipole moment and the relationship between the modes we observe and the transverse and longitudinal resonances associated with the excitonic response. We also investigate why this type of double splitting is rarely observed in experiments.

Strong Coupling beyond the Light-Line.

Strong coupling of molecules placed in an optical microcavity may lead to the formation of hybrid states called polaritons; states that inherit characteristics of both the optical cavity modes and the molecular resonance. Developing a better understanding of the matter characteristics of these hybrid states has been the focus of much recent attention. Here, as we will show, a better understanding of the role of the optical modes supported by typical cavity structures is also required. Typical microcavities used in molecular strong coupling experiments support more than one mode at the frequency of the material resonance. While the effect of strong coupling to multiple photonic modes has been considered before, here we extend this topic by looking at strong coupling between one vibrational mode and multiple photonic modes. Many experiments involving strong coupling make use of metal-clad microcavities, ones with metallic mirrors. Metal-clad microcavities are well-known to support coupled plasmon modes in addition to the standard microcavity mode. However, the coupled plasmon modes associated with a metal-clad optical microcavity lie beyond the light-line and are thus not probed in typical experiments on strong coupling. Here we investigate, through experiment and numerical modeling, the interaction between molecules within a cavity and the modes both inside and outside the light-line. Making use of grating coupling and a metal-clad microcavity, we provide an experimental demonstration that such modes undergo strong coupling. We further show that a common variant of the metal-clad microcavity, one in which the metal mirrors are replaced by distributed Bragg reflector also show strong coupling to modes that exist in these structures beyond the light-line. Our results highlight the need to consider the effect of beyond the light-line modes on the strong coupling of molecular resonances in microcavities and may be of relevance in designing strong coupling resonators for chemistry and materials science investigations.

A New Signature for Strong Light-Matter Coupling Using Spectroscopic Ellipsometry.

Light-matter interactions can occur when an ensemble of molecular resonators is placed in a confined electromagnetic field. In the strong coupling regime the rapid exchange of energy between the molecules and the electromagnetic field results in the emergence of hybrid light-matter states called polaritons. Multiple criteria exist to define the strong coupling regime, usually by comparing the splitting of the polariton bands with the line widths of the uncoupled modes. Here, we highlight the limitations of these criteria and study strong coupling using spectroscopic ellipsometry, a commonly used optical characterization technique. We identify a new signature of strong coupling in ellipsometric phase spectra. The combination of ellipsometric amplitude and phase spectra yields a distinct topological feature that we suggest could serve as a new criterion for strong coupling. Our results introduce the idea of ellipsometric topology and could provide further insight into the transition from the weak to strong coupling regime.

Molecular Monolayer Strong Coupling in Dielectric Soft Microcavities.

We report strong coupling of a monolayer of J-aggregated dye molecules to the whispering gallery modes of a dielectric microsphere at room temperature. We systematically studied the evolution of strong coupling as the number of layers of dye molecules was increased and found the Rabi splitting to rise from 56 meV for a single layer to 94 meV for four layers of dye molecules. We compare our experimental results with two-dimensional (2D) numerical simulations and a simple coupled oscillator model, finding good agreement. We anticipate that these results will act as a stepping stone for integrating molecule-cavity strong coupling in a microfluidic environment since microspheres can be easily trapped and manipulated in such an environment and provide open access cavities.