Influence of Quadrupolar Molecular Transitions within Plasmonic Cavities.

Optical nanocavities have revolutionized the manipulation of radiative properties of molecular and semiconductor emitters. Here, we investigate the amplified photoluminescence arising from exciting a dark transition of ß-carotene molecules embedded within plasmonic nanocavities. Integrating a molecular monolayer into nanoparticle-on-mirror nanostructures unveils enhancements surpassing 4 orders of magnitude in the initially light-forbidden excitation. Such pronounced enhancements transcend conventional dipolar mechanisms, underscoring the presence of alternative enhancement pathways. Notably, Fourier-plane scattering spectroscopy shows that the photoluminescence excitation resonance aligns with a higher-order plasmonic cavity mode, which supports strong field gradients. Combining quantum chemistry calculations with electromagnetic simulations reveals an important interplay between the Franck-Condon quadrupole and Herzberg-Teller dipole contributions in governing the absorption characteristics of this dark transition. In contrast to free space, the quadrupole moment plays a significant role in photoluminescence enhancement within nanoparticle-on-mirror cavities. These findings provide an approach to access optically inactive transitions, promising advancements in spectroscopy and sensing applications.

Unconventional magnetism mediated by spin-phonon-photon coupling.

Magnetic order typically emerges due to the short-range exchange interaction between the constituent electronic spins. Recent discoveries have found a crucial role for spin-phonon coupling in various phenomena from optical ultrafast magnetization switching to dynamical control of the magnetic state. Here, we demonstrate theoretically the emergence of a biquadratic long-range interaction between spins mediated by their coupling to phonons hybridized with vacuum photons into polaritons. The resulting ordered state enabled by the exchange of virtual polaritons between spins is reminiscent of superconductivity mediated by the exchange of virtual phonons. The biquadratic nature of the spin-spin interaction promotes ordering without favoring ferro- or antiferromagnetism. It further makes the phase transition to magnetic order a first-order transition, unlike in conventional magnets. Consequently, a large magnetization develops abruptly on lowering the temperature which could enable magnetic memories admitting ultralow-power thermally-assisted writing while maintaining a high data stability. The role of photons in the phenomenon further enables an in-situ static control over the magnetism. These unique features make our predicted spin-spin interaction and magnetism highly unconventional paving the way for novel scientific and technological opportunities.

Lindblad Master Equation Capable of Describing Hybrid Quantum Systems in the Ultrastrong Coupling Regime.

Despite significant theoretical efforts devoted to studying the interaction between quantized light modes and matter, the so-called ultrastrong coupling regime still presents significant challenges for theoretical treatments and prevents the use of many common approximations. Here we demonstrate an approach that can describe the dynamics of hybrid quantum systems in any regime of interaction for an arbitrary electromagnetic (EM) environment. We extend a previous method developed for few-mode quantization of arbitrary systems to the case of ultrastrong light-matter coupling, and show that even such systems can be treated using a Lindblad master equation where decay operators act only on the photonic modes by ensuring that the effective spectral density of the EM environment is sufficiently suppressed at negative frequencies. We demonstrate the validity of our framework and show that it outperforms current state-of-the-art master equations for a simple model system, and then study a realistic nanoplasmonic setup where existing approaches cannot be applied.

Strong Light-Matter Coupling in Lead Halide Perovskite Quantum Dot Solids.

Strong coupling between lead halide perovskite materials and optical resonators enables both polaritonic control of the photophysical properties of these emerging semiconductors and the observation of fundamental physical phenomena. However, the difficulty in achieving optical-quality perovskite quantum dot (PQD) films showing well-defined excitonic transitions has prevented the study of strong light-matter coupling in these materials, central to the field of optoelectronics. Herein we demonstrate the formation at room temperature of multiple cavity exciton-polaritons in metallic resonators embedding highly transparent Cesium Lead Bromide quantum dot (CsPbBr3-QD) solids, revealed by a significant reconfiguration of the absorption and emission properties of the system. Our results indicate that the effects of biexciton interaction or large polaron formation, frequently invoked to explain the properties of PQDs, are seemingly absent or compensated by other more conspicuous effects in the CsPbBr3-QD optical cavity. We observe that strong coupling enables a significant reduction of the photoemission line width, as well as the ultrafast modulation of the optical absorption, controllable by means of the excitation fluence. We find that the interplay of the polariton states with the large dark state reservoir plays a decisive role in determining the dynamics of the emission and transient absorption properties of the hybridized light-quantum dot solid system. Our results should serve as the basis for future investigations of PQD solids as polaritonic materials.

Multi-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling.

Exciton transport can be enhanced in the strong coupling regime where excitons hybridize with confined light modes to form polaritons. Because polaritons have group velocity, their propagation should be ballistic and long-ranged. However, experiments indicate that organic polaritons propagate in a diffusive manner and more slowly than their group velocity. Here, we resolve this controversy by means of molecular dynamics simulations of Rhodamine molecules in a Fabry-Pérot cavity. Our results suggest that polariton propagation is limited by the cavity lifetime and appears diffusive due to reversible population transfers between polaritonic states that propagate ballistically at their group velocity, and dark states that are stationary. Furthermore, because long-lived dark states transiently trap the excitation, propagation is observed on timescales beyond the intrinsic polariton lifetime. These insights not only help to better understand and interpret experimental observations, but also pave the way towards rational design of molecule-cavity systems for coherent exciton transport.

Can We Observe Nonperturbative Vacuum Shifts in Cavity QED?

We address the fundamental question of whether or not it is possible to achieve conditions under which the coupling of a single dipole to a strongly confined electromagnetic vacuum can result in nonperturbative corrections to the dipole's ground state. To do so we consider two simplified, but otherwise rather generic cavity QED setups, which allow us to derive analytic expressions for the total ground-state energy and to distinguish explicitly between purely electrostatic and genuine vacuum-induced contributions. Importantly, this derivation takes the full electromagnetic spectrum into account while avoiding any ambiguities arising from an ad hoc mode truncation. Our findings show that while the effect of confinement per se is not enough to result in substantial vacuum-induced corrections, the presence of high-impedance modes, such as plasmons or engineered LC resonances, can drastically increase these effects. Therefore, we conclude that with appropriately designed experiments it is at least in principle possible to access a regime where light-matter interactions become nonperturbative.

Non-Hermitian Anharmonicity Induces Single-Photon Emission.

Single-photon sources are in high demand for quantum information applications. A paradigmatic way to achieve single-photon emission is through anharmonicity in the energy levels, such that the absorption of a single photon from a coherent drive shifts the system out of resonance and prevents absorption of a second one. We identify a novel mechanism for single-photon emission through non-Hermitian anharmonicity, i.e., anharmonicity in the losses instead of in the energy levels. We demonstrate the mechanism in two types of systems, including a feasible setup consisting of a hybrid metallodielectric cavity weakly coupled to a two-level emitter, and show that it induces high-purity single-photon emission at high repetition rates.

Quantitative Investigation of the Rate of Intersystem Crossing in the Strong Exciton-Photon Coupling Regime.

Strong interactions between excitons and photons lead to the formation of exciton-polaritons, which possess completely different properties compared to their constituents. The polaritons are created by incorporating a material in an optical cavity where the electromagnetic field is tightly confined. Over the last few years, the relaxation of polaritonic states has been shown to enable a new kind of energy transfer event, which is efficient at length scales substantially larger than the typical Förster radius. However, the importance of such energy transfer depends on the ability of the short-lived polaritonic states to efficiently decay to molecular localized states that can perform a photochemical process, such as charge transfer or triplet states. Here, we investigate quantitatively the interaction between polaritons and triplet states of erythrosine B in the strong coupling regime. We analyze the experimental data, collected mainly employing angle-resolved reflectivity and excitation measurements, using a rate equation model. We show that the rate of intersystem crossing from the polariton to the triplet states depends on the energy alignment of the excited polaritonic states. Furthermore, it is demonstrated that the rate of intersystem crossing can be substantially enhanced in the strong coupling regime to the point where it approaches the rate of the radiative decay of the polariton. In light of the opportunities that transitions from polaritonic to molecular localized states offer within molecular photophysics/chemistry and organic electronics, we hope that the quantitative understanding of such interactions gained from this study will aid in the development of polariton-empowered devices.

Few-mode field quantization for multiple emitters.

The control of the interaction between quantum emitters using nanophotonic structures holds great promise for quantum technology applications, while its theoretical description for complex nanostructures is a highly demanding task as the electromagnetic (EM) modes form a high-dimensional continuum. We here introduce an approach that permits a quantized description of the full EM field through a small number of discrete modes. This extends the previous work in ref. (I. Medina, F. J. García-Vidal, A. I. Fernández-Domínguez, and J. Feist, "Few-mode field quantization of arbitrary electromagnetic spectral densities," Phys. Rev. Lett., vol. 126, p. 093601, 2021) to the case of an arbitrary number of emitters, without any restrictions on the emitter level structure or dipole operators. The low computational demand of this method makes it suitable for studying dynamics for a wide range of parameters. We illustrate the power of our approach for a system of three emitters placed within a hybrid metallodielectric photonic structure and show that excitation transfer is highly sensitive to the properties of the hybrid photonic-plasmonic modes.

A Theoretical Perspective on Molecular Polaritonics.

In the past decade, much theoretical research has focused on studying the strong coupling between organic molecules (or quantum emitters, in general) and light modes. The description and prediction of polaritonic phenomena emerging in this light-matter interaction regime have proven to be difficult tasks. The challenge originates from the enormous number of degrees of freedom that need to be taken into account, both in the organic molecules and in their photonic environment. On one hand, the accurate treatment of the vibrational spectrum of the former is key, and simplified quantum models are not valid in many cases. On the other hand, most photonic setups have complex geometric and material characteristics, with the result that photon fields corresponding to more than just a single electromagnetic mode contribute to the light-matter interaction in these platforms. Moreover, loss and dissipation, in the form of absorption or radiation, must also be included in the theoretical description of polaritons. Here, we review and offer our own perspective on some of the work recently done in the modeling of interacting molecular and optical states with increasing complexity.

Not dark yet for strong light-matter coupling to accelerate singlet fission dynamics.

Polaritons are unique hybrid light-matter states that offer an alternative way to manipulate chemical processes. In this work, we show that singlet fission dynamics can be accelerated under strong light-matter coupling. For superexchange-mediated singlet fission, state mixing speeds up the dynamics in cavities when the lower polariton is close in energy to the multiexcitonic state. This effect is more pronounced in non-conventional singlet fission materials in which the energy gap between the bright singlet exciton and the multiexcitonic state is large ( > 0.1 eV). In this case, the dynamics is dominated by the polaritonic modes and not by the bare-molecule-like dark states, and, additionally, the resonant enhancement due to strong coupling is robust even for energetically broad molecular states. The present results provide a new strategy to expand the range of suitable materials for efficient singlet fission by making use of strong light-matter coupling.

Theoretical Challenges in Polaritonic Chemistry.

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. While in wavelength-scale optical cavities the 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 theoretical toolbox is then required to explore the rich phenomenology of polaritonic chemistry. Within this framework, each component of the system (molecules and electromagnetic modes) needs to be treated in sufficient detail to obtain reliable results. Starting from the very general aspects of light-molecule interactions in typical experimental setups, we underline the basic concepts that should be taken into account when operating in this new area of research. Building on these considerations, we then provide a map of the theoretical tools already available to tackle chemical applications of molecular polaritons at different scales. Throughout the discussion, we draw attention to both the successes and the challenges still ahead in the theoretical description of polaritonic chemistry.

Plexcitonic Quantum Light Emission from Nanoparticle-on-Mirror Cavities.

We investigate the quantum-optical properties of the light emitted by a nanoparticle-on-mirror cavity filled with a single quantum emitter. Inspired by recent experiments, we model a dark-field setup and explore the photon statistics of the scattered light under grazing laser illumination. Exploiting analytical solutions to Maxwell's equations, we quantize the nanophotonic cavity fields and describe the formation of plasmon-exciton polaritons (or plexcitons) in the system. This way, we reveal that the rich plasmonic spectrum of the nanocavity offers unexplored mechanisms for nonclassical light generation that are more efficient than the resonant interaction between the emitter natural transition and the brightest optical mode. Specifically, we find three different sample configurations in which strongly antibunched light is produced. Finally, we illustrate the power of our approach by showing that the introduction of a second emitter in the platform can enhance photon correlations further.

Selective isomer emission via funneling of exciton polaritons.

Polaritons in organic systems has shown the potential to modify chemical properties and to mediate long-range energy transfer between individual chromophores, among other capabilities. Here, we demonstrate that strong coupling and formation of organic exciton-polaritons can be used to selectively tune the isomer emission of organic molecules. By taking advantage of their delocalized and hybrid character, polaritons emerging in the strong coupling regime open a new relaxation pathway that allows for an efficient funneling of the excitation between the molecular isomers. We implement this by strong coupling to trans-DCS (E-4-dimethylamino-4'cyanostilbene)molecules, which present two isomers in different amounts when immersed in a polymer matrix. Thanks to this new relaxation pathway, the photoexcitation that is first shared by the common polaritonic mode is then selectively funneled to the excited states of one of the isomers, recognizing pure emission from the isomeric states that do not contribute to emission under normal conditions.

Ultrastrong Exciton-Photon Coupling in Broadband Solar Absorbers.

The recent development of organic polaritonic solar cells, in which sunlight absorbers and photon modes of a resonator are hybridized as a result of their strong coupling, has revealed the potential this interaction offers to control and enhance the performance of these devices. In this approach, the photovoltaic cell is built in such a way that it also behaves as an optical cavity supporting spectrally well-defined resonances, which match the broad absorption bands of the dyes employed. Herein we focus on the experimental and theoretical analysis of the specific spectral and angular optical absorption characteristics of a broadband light harvester, namely a subphthalocyanine, when operating in the ultrastrong coupling regime. We discuss the implications of having a broad distribution of oscillator strengths and demonstrate that rational design of the layered structure is needed to optimize both the spectral and the angular response of the sunlight harvester dye.

Accurate Truncations of Chain Mapping Models for Open Quantum Systems.

The dynamics of open quantum systems are of great interest in many research fields, such as for the interaction of a quantum emitter with the electromagnetic modes of a nanophotonic structure. A powerful approach for treating such setups in the non-Markovian limit is given by the chain mapping where an arbitrary environment can be transformed to a chain of modes with only nearest-neighbor coupling. However, when long propagation times are desired, the required long chain lengths limit the utility of this approach. We study various approaches for truncating the chains at manageable lengths while still preserving an accurate description of the dynamics. We achieve this by introducing losses to the chain modes in such a way that the effective environment acting on the system remains unchanged, using a number of different strategies. Furthermore, we demonstrate that extending the chain mapping to allow next-nearest neighbor coupling permits the reproduction of an arbitrary environment, and adding longer-range interactions does not further increase the effective number of degrees of freedom in the environment.

Few-Mode Field Quantization of Arbitrary Electromagnetic Spectral Densities.

We develop a framework that provides a few-mode master equation description of the interaction between a single quantum emitter and an arbitrary electromagnetic environment. The field quantization requires only the fitting of the spectral density, obtained through classical electromagnetic simulations, to a model system involving a small number of lossy and interacting modes. We illustrate the power and validity of our approach by describing the population and electric field spatial dynamics in the spontaneous decay of an emitter placed in a complex hybrid plasmonic-photonic structure.

Multi-scale dynamics simulations of molecular polaritons: The effect of multiple cavity modes on polariton relaxation.

Coupling molecules to the confined light modes of an optical cavity is showing great promise for manipulating chemical reactions. However, to fully exploit this principle and use cavities as a new tool for controlling chemistry, a complete understanding of the effects of strong light-matter coupling on molecular dynamics and reactivity is required. While quantum chemistry can provide atomistic insight into the reactivity of uncoupled molecules, the possibilities to also explore strongly coupled systems are still rather limited due to the challenges associated with an accurate description of the cavity in such calculations. Despite recent progress in introducing strong coupling effects into quantum chemistry calculations, applications are mostly restricted to single or simplified molecules in ideal lossless cavities that support a single light mode only. However, even if commonly used planar mirror micro-cavities are characterized by a fundamental mode with a frequency determined by the distance between the mirrors, the cavity energy also depends on the wave vector of the incident light rays. To account for this dependency, called cavity dispersion, in atomistic simulations of molecules in optical cavities, we have extended our multi-scale molecular dynamics model for strongly coupled molecular ensembles to include multiple confined light modes. To validate the new model, we have performed simulations of up to 512 Rhodamine molecules in red-detuned Fabry-Pérot cavities. The results of our simulations suggest that after resonant excitation into the upper polariton at a fixed wave vector, or incidence angle, the coupled cavity-molecule system rapidly decays into dark states that lack dispersion. Slower relaxation from the dark state manifold into both the upper and lower bright polaritons causes observable photo-luminescence from the molecule-cavity system along the two polariton dispersion branches that ultimately evolves toward the bottom of the lower polariton branch, in line with experimental observations. We anticipate that the more realistic cavity description in our approach will help to better understand and predict how cavities can modify molecular properties.

Molecular photodissociation enabled by ultrafast plasmon decay.

We propose a strategy for enabling photodissociation of a normally photostable molecule through coupling to a nanoparticle plasmon. The large possible coupling on the single-molecule level combined with the highly lossy nature of plasmonic modes, with lifetimes on the order of femtoseconds, opens an ultrafast decay channel for the molecule. For plasmon mode frequencies below the vertical photoexcitation energy of the molecule, the difference between the excitation and emission energies is converted into vibrational energy on the molecular ground state in a Raman-like process. Under the correct conditions, this energy can be high enough to enable efficient photodissociation on the electronic ground state. We demonstrate the concept using numerical simulations of the Lindblad master equation for the hydrogen molecule in the vicinity of an aluminum nanoparticle and explore the photodissociation efficiency as a function of various system parameters.