Polaritonic chemistry has become a rapidly developing field within the last few years. A multitude of experimental observations suggest that chemical properties can be fundamentally altered and novel physical states appear when matter is strongly coupled to resonant cavity modes, i.e. when hybrid light-matter states emerge. Up until now, theoretical approaches to explain and predict these observations were either limited to phenomenological quantum optical models, suited to describe collective polaritonic effects, or alternatively to ab initio approaches for small system sizes. The later methods were particularly controversial since collective effects could not be explicitly included due to the intrinsically low particle numbers, which are computationally accessible. Here, we demonstrate for a nitrogen dimer chain of variable size that any impurity present in a collectively coupled chemical ensemble (e.g. temperature fluctuations or reaction process) induces local modifications in the polaritonic system. From this we deduce that a novel dark state is formed, whose local chemical properties are modified considerably at the impurity due to the collectively coupled environment. Our simulations unify theoretical predictions from quantum optical models (e.g. formation of collective dark states and different polaritonic branches) with the single molecule quantum chemical perspective, which relies on the (quantized) redistribution of local charges. Moreover, our findings suggest that the recently developed QEDFT method is suitable to access these locally scaling polaritonic effects and it is a useful tool to better understand recent experimental results and to even design novel experimental approaches. All of which paves the way for many novel discoveries and applications in polaritonic chemistry.
The second law of photochemistry states that in most cases, no more than one molecule is activated for an excited-state reaction for each photon absorbed by a collection of molecules. In this work, we demonstrate that it is possible to trigger a many-molecule reaction using only one photon by strongly coupling the molecular ensemble to a confined light mode. The collective nature of the resulting hybrid states of the system (the so-called polaritons) leads to the formation of a polaritonic "supermolecule" involving the degrees of freedom of all molecules, opening a reaction path on which all i…
Polaritonic chemistry exploits strong light-matter coupling between molecules and confined electromagnetic field modes to enable new chemical reactivities. In systems displaying this functionality, the choice of the cavity determines both the confinement of the electromagnetic field and the number of molecules that are involved in the process, whereas in wavelength-scale optical cavities light-matter interaction is ruled by collective effects, plasmonic subwavelength nanocavities allow even single molecules to reach strong coupling. Due to these very distinct situations, a multiscale theoretic…
The spectral characteristics of near-field thermal emission from nanoparticle arrays are explained by comparison to the dispersions for propagating modes. Using the coupled dipole model, we analytically calculate the spectral emission from single particles, chains, planes, and 3D arrays of SiO2 and SiC. We show that the differences in their spectra are due to the existence or absence of propagating surface phonon polariton modes and that the emission is dominated by these modes when they are present. This work paves the way for understanding and control of near-field radiation in nanofluids, n…
Systems with strong light-matter interaction opens up new avenues for studying topological phases of matter. Examples include exciton-polaritons, mixed light-matter quasiparticles, where the topology of the polaritonic band structure arises from the collective coupling between matter wave and optical fields strongly confined in periodic dielectric structures. Distinct from light-matter interaction in a uniform environment, the spatially varying nature of the optical fields leads to a fundamental modification of the well-known optical selection rules, which were derived under the plane wave app…
Rayleigh scattering is usually considered to be the elastic scattering of photons from sub-wavelength physical objects, such as small particles or molecules. Here, we present the spectroscopic study of the scattering properties of molecules embedded in an optical cavity under strong coupling conditions, where the collective interaction between the molecules and the cavity gives rise to composite light-matter excitations known as cavity polaritons. We show that the polaritonic states exhibit strong resonant Rayleigh scattering, reaching 25% efficiency. Since the polaritonic wavefunctions in suc…
We study the dependence of the vacuum Rabi splitting (VRS) on frequency disorder, vibrations, near-field effects and density in molecular polaritonics. In the mesoscopic limit, static frequency disorder alone can already introduce a loss mechanism from polaritonic states into a dark state reservoir, which we quantitatively describe, providing an analytical scaling of the VRS with the level of disorder. Disorder additionally can split a molecular ensemble into donor-type and acceptor-type molecules and the combination of vibronic coupling, dipole-dipole interactions and vibrational relaxation i…
Chemical manifestations of strong light-matter coupling have been recently subject of intense experimental and theoretical studies. Here we review the present status of this field. Section 1 is an introduction to molecular polaritonics and to collective response aspects of light-matter interactions. Section 2 provides an overview of the key experimental observations of these effects while Section 3 describe our current theoretical understanding of the effect of strong light-matter coupling on chemical dynamics. A brief outline of applications to energy conversion processes in given in Section …
We revisited the intersubband polaritonics - the branch of mesoscopic physics having a huge potential for optoelectronic applications in the infrared and terahertz domains - and found that, contrary to the general opinion, the Coulomb interactions play crucial role in the processes of light-matter coupling in the considered systems. Electron-electron and electron-hole interactions radically change the nature of the elementary excitations in these systems. We show that intersubband polaritons represent the result of the coupling of a photonic mode with collective excitations, and not non-intera…
The coherent interaction of a large collection of molecules with a common photonic mode results in strong light-matter coupling, a feature that proved highly beneficial for chemistry and termed the research topics polaritonic and QED chemistry. Considering complex microscopic chemical reactions in combination with a macroscopic number of molecules renders existing ab initio approaches inapplicable. In this work, I introduce a simple approach to capture the collective nature while retaining the full ab initio representation of single molecules. By embedding the majority of the molecular ensembl…
The formation of hybrid light-molecule states (polaritons) offers a new strategy to manipulate the photochemistry of molecules. To fully exploit its potential, one needs to build a toolbox of polaritonic phenomenologies that supplement those of standard photochemistry. By means of a state-of-the-art computational photochemistry approach extended to the strong-coupling regime, here we disclose various mechanisms peculiar of polaritonic chemistry: coherent population oscillations between polaritons, quenching by trapping in dead-end polaritonic states and the alteration of the photochemical reac…
When a collection of quantum emitters interacts with an electromagnetic field, the whole system can enter into the collective strong coupling regime in which hybrid light-matter states, i.e., polaritons can be created. Only a small portion of excitations in the emitters are coupled to the light field, and there are many dark states that, in principle, retain their pure excitonic nature. Here we theoretically demonstrate that these dark states can have a delocalized character, which is inherent to polaritons, despite the fact that they do not have a photonic component. This unexpected behavior …
Manipulation of chemical reactivity often involves changing reagents or environmental conditions. Alternatively, strong coupling between light and matter offers a way to tunably hybridize their physicochemical properties and thereby change reaction dynamics without synthetic modifications to the starting material. Here, we theoretically design a polaritonic (hybrid photonic-molecular) device that supports ultrafast tuning of reaction yields even when the catalyst and its reactant are spatially separated across several optical wavelengths. We demonstrate how photoexcitation of a `remote catalys…
We investigate theoretically the coupling of a cavity mode to a continuous distribution of emitters. We discuss the influence of the emitters inhomogeneous broadening on the existence and on the coherence properties of the polaritonic peaks. We find that their coherence depends crucially on the shape of the distribution and not only on its width. Under certain conditions the coupling to the cavity protects the polaritonic states from inhomogeneous broadening, resulting in a longer storage time for a quantum memory based on emitters ensembles. When two different ensembles of emitters are couple…
Achieving and controlling strong light-matter interactions in many-body systems is of paramount importance both for fundamental understanding and potential applications. In this paper we demonstrate both experimentally and theoretically how to manipulate strong coupling between the Bragg-plasmon mode supported by a organo-metallic array and molecular excitons in the form of J-aggregates dispersed on the hybrid structure. We observe experimentally the transition from a conventional strong coupling regime exhibiting the usual upper and lower polaritonic branches to a more complex regime, where a…
Recent experimental advances enable the fabrication of photonic lattices in which the light propagates with non-trivial energy dispersions. When interfaced with quantum emitters, such systems yield strong collective spontaneous emission phenomena, such as perfect sub-radiance, in which the decay into the bath is completely suppressed, forming bound-states-in-the-continuum. Since such photonic lattices are generally lossy, an alternative way of probing them consists in coherently driving them to an steady-state from which photoluminescence can be extracted. Here, we formalize connections betwee…
We demonstrate that exciton conductance in organic materials can be enhanced by several orders of magnitude when the molecules are strongly coupled to an electromagnetic mode. Using a 1D model system, we show how the formation of a collective polaritonic mode allows excitons to bypass the disordered array of molecules and jump directly from one end of the structure to the other. This finding could have important implications in the fields of exciton transistors, heat transport, photosynthesis, and biological systems in which exciton transport plays a key role.
Confined electromagnetic modes strongly couple to collective excitations in ensembles of quantum emitters, producing light-matter hybrid states known as polaritons. Under such conditions, the discrete multilevel spectrum of molecular systems offers an appealing playground for exploring multiphoton processes. This work contrasts predictions from the Tavis-Cummings (TC) model, in which the material is a collection of two-level systems, with the implications of considering additional energy levels with harmonic and anharmonic structures. We discuss the exact eigenspectrum, up to the second excita…
A quantum simulation of vibrational strong coupling (VSC) in the collective regime via thermostatted ring-polymer molecular dynamics (TRPMD) is reported. For a collection of liquid-phase water molecules resonantly coupled to a single lossless cavity mode, the simulation shows that, as compared with a fully classical calculation, the inclusion of nuclear and photonic quantum effects does not lead to a change in the Rabi splitting but does broaden polaritonic linewidths roughly by a factor of two. Moreover, under thermal equilibrium, both quantum and classical simulations predict that the static…
Can we couple multiple molecular species to soft-cavities? The answer to this question has relevance in designing open cavities for polaritonic chemistry applications. Due to 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, using a layer-by-layer deposition technique onto a dielectric microsphere so as to facilitate the multi molecule coupling. We observed the formation of a middle polariton branch due to the inter-molecular mi…
