Influence of Quadrupolar Molecular Transitions within Plasmonic Cavities (PDF)
J. Huang, O. S. Ojambati, C. Climent, A. Cuartero-Gonzalez, E. Elliott, J. Feist, A. I. Fernández-Domínguez, and J. J. Baumberg
Unconventional magnetism mediated by spin-phonon-photon coupling (PDF)
P. A. Pantazopoulos, J. Feist, F. J. García-Vidal, and A. Kamra
Strong Light–Matter Coupling in Lead Halide Perovskite Quantum Dot Solids (PDF)
C. Bujalance, L. Caliò, D. N. Dirin, D. O. Tiede, J. F. Galisteo-López, J. Feist, F. J. García-Vidal, M. V. Kovalenko, and H. Míguez
Abstract: ...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.


Vacuum-field-induced state mixing (PDF)
D. Fernández de la Pradilla, E. Moreno, and J. Feist
Quantitative Investigation of the Rate of Intersystem Crossing in the Strong Exciton–Photon Coupling Regime (PDF)
A. Mukherjee, J. Feist, and K. Börjesson
Abstract: ...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.


Theoretical Challenges in Polaritonic Chemistry (PDF)
J. Fregoni, F. J. Garcia-Vidal, and J. Feist


Reply to the Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments”
C. Climent and J. Feist
Cavity-modified Chemistry: Towards Vacuum-field Catalysis
C. Climent, F. J. Garcia-Vidal, and J. Feist
Abstract: ...In the preceding chapters, electric field effects on chemical reactivity have been extensively discussed, focusing on STM setups and enzyme catalysis among many others. Here we will focus on a rather different and only recently explored approach to manipulate chemical reactions with electric fields. With the use of resonant cavity modes hosted in Fabry–Pérot cavities for instance, as well as plasmonic modes, very recent investigations have shown modifications of chemical reactivity and dynamics, including thermal reactions and photochemistry, as well as manipulation of materials properties and non-adiabatic processes. All these works have given birth to a new field termed polaritonic chemistry due to the fact that in the so-called strong-coupling regime, polaritons become the new eigenstates of the system. These are hybrid states of light and matter that inherit properties from both constituents, providing new means to modify chemical phenomena. The aim of this chapter is two-fold: on one side, we aim to provide a general background on confined light modes and strong coupling for the non-specialised reader, and on the other, we aim to review the recent achievements of the field, paying special attention to modifications in ground-state reactivity. To this end, the chapter is organised as follows. After an introduction to settle basic concepts, we review the most relevant experimental and theoretical work in which modified chemical reactivity has been reported and conclude with the challenges faced by the field.
Photoisomerization Efficiency of a Solar Thermal Fuel in the Strong Coupling Regime (PDF)
J. Mony, C. Climent, A. U. Petersen, K. Moth-Poulsen, J. Feist, and K. Börjesson
Multi-scale dynamics simulations of molecular polaritons: The effect of multiple cavity modes on polariton relaxation (PDF)
R. H. Tichauer, J. Feist, and G. Groenhof
Abstract: ...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.


On the SN2 reactions modified in vibrational strong coupling experiments: reaction mechanisms and vibrational mode assignments (PDF)
C. Climent and J. Feist
Abstract: ...Recent experiments have reported modified chemical reactivity under vibrational strong coupling (VSC) in microfluidic Fabry–Pérot cavities. In particular, the reaction rate of nucleophilic substitution reactions at silicon centers (SN2@Si) has been altered when a vibrational mode of the reactant was coupled to a confined light mode in the strong coupling regime. In this situation, hybrid light–matter states known as polaritons are formed and seem to be responsible for the modified chemical kinetics. These results are very encouraging for future applications of polaritonic chemistry to catalyze chemical reactions, with the ability to manipulate chemical phenomena without any external excitation of the system. Still, there is no theory capable of explaining the mechanism behind these results. In this work we address two points that are crucial for the interpretation of these experiments. Firstly, by means of electronic structure calculations we report the reaction mechanism in normal conditions of the two recently modified SN2@Si reactions, obtaining in both cases a triple-well PES where the rate-determining step is due to the Si–C and Si–O bond cleavage. Secondly, we characterize in detail the normal modes of vibration of the reactants. In the VSC experiments, reaction rates were modified only when specific vibrations of the reactants were coupled to a cavity mode. We find that these vibrations are highly mixed among the different fragments of the reactants leading to a completely new assignment of the IR peaks coupled to cavity modes in the original experimental works. Our results are fundamental for the interpretation of the VSC experiments given that in the absence of a theory explaining these results, the current phenomenological understanding relies on the assignment of the character of the vibrational IR peaks.
Photoprotecting Uracil by Coupling with Lossy Nanocavities (PDF)
S. Felicetti, J. Fregoni, T. Schnappinger, S. Reiter, R. de Vivie-Riedle, and J. Feist
Cumulant expansion for the treatment of light-matter interactions in arbitrary material structures (PDF)
M. Sánchez-Barquilla, R. E. F. Silva, and J. Feist


Tracking Polariton Relaxation with Multiscale Molecular Dynamics Simulations (PDF)
G. Groenhof, C. Climent, J. Feist, D. Morozov, and J. J. Toppari
Abstract: ...When photoactive molecules interact strongly with confined light modes in optical cavities, new hybrid light–matter states form. They are known as polaritons and correspond to coherent superpositions of excitations of the molecules and of the cavity photon. The polariton energies and thus potential energy surfaces are changed with respect to the bare molecules, such that polariton formation is considered a promising paradigm for controlling photochemical reactions. To effectively manipulate photochemistry with confined light, the molecules need to remain in the polaritonic state long enough for the reaction on the modified potential energy surface to take place. To understand what determines this lifetime, we have performed atomistic molecular dynamics simulations of room-temperature ensembles of rhodamine chromophores strongly coupled to a single confined light mode with a 15 fs lifetime. We investigated three popular experimental scenarios and followed the relaxation after optically pumping (i) the lower polariton, (ii) the upper polariton, or (iii) uncoupled molecular states. The results of the simulations suggest that the lifetimes of the optically accessible lower and upper polaritons are limited by (i) ultrafast photoemission due to the low cavity lifetime and (ii) reversible population transfer into the “dark” state manifold. Dark states are superpositions of molecular excitations but with much smaller contributions from the cavity photon, decreasing their emission rates and hence increasing their lifetimes. We find that population transfer between polaritonic modes and dark states is determined by the overlap between the polaritonic and molecular absorption spectra. Importantly, excitation can also be transferred ”upward” from the lower polariton into the dark-state reservoir due to the broad absorption spectra of the chromophores, contrary to the common conception of these processes as a ”one-way” relaxation from the dark states down to the lower polariton. Our results thus suggest that polaritonic chemistry relying on modified dynamics taking place within the lower polariton manifold requires cavities with sufficiently long lifetimes and, at the same time, strong light–matter coupling strengths to prevent the back-transfer of excitation into the dark states.
Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity (PDF)
J. Galego, C. Climent, F. J. Garcia-Vidal, and J. Feist
Abstract: ...Here, we present a fundamental study on how the ground-state chemical reactivity of a single molecule can be modified in a QED scenario, i.e., when it is placed inside a nanoscale cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a model system for the molecule (Shin-Metiu model) in which nuclear, electronic, and photonic degrees of freedom are treated on the same footing. This simplified model allows the comparison of exact quantum reaction rate calculations with predictions emerging from transition state theory based on the cavity Born-Oppenheimer approach. We demonstrate that QED effects are indeed able to significantly modify activation barriers in chemical reactions and, as a consequence, reaction rates. The critical physical parameter controlling this effect is the permanent dipole of the molecule and how this magnitude changes along the reaction coordinate. We show that the effective coupling can lead to significant single-molecule energy shifts in an experimentally available nanoparticle-on-mirror cavity. We then apply the validated theory to a realistic case (internal rotation in the 1,2-dichloroethane molecule), showing how reactions can be inhibited or catalyzed depending on the profile of the molecular dipole. Furthermore, we discuss the absence of resonance effects in the present scenario, which can be understood through its connection to Casimir-Polder forces. Finally, we treat the case of many-molecule strong coupling and find collective modifications of reaction rates if the molecular permanent dipole moments are oriented with respect to the cavity field.