Emergent Properties When Molecules Meet the Electromagnetic Vacuum Field
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Emergent Properties When Molecules Meet the Electromagnetic Vacuum Field
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ACS Applied Optical Materials

Cite this: ACS Appl. Opt. Mater. 2025, 3, 11, 2435–2445
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https://doi.org/10.1021/acsaom.5c00375
Published November 11, 2025

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Abstract

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The strong coupling of molecular transition dipoles to the electromagnetic vacuum field unlocks unique possibilities in chemistry and materials science. The half-light, half-matter characteristics of the polaritonic states have been effective in promoting transport, modifying molecular photophysics, driving chemical reactions, and assembling molecules. However, the impact of electronic and vibrational strong couplings on the intermolecular interactions is rarely discussed. Here, we briefly overview energy- and charge-transport properties modified under electronic and vibrational strong coupling conditions. We discuss how strong coupling can induce changes to molecular assemblies and affect the photophysics of molecular systems. Further, we provide a perspective on the cavity-altered molecular properties by connecting them to cavity-modified molecular interactions.

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1. Introduction

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The semiclassical picture of light–matter interaction focuses on how oscillating electromagnetic (EM) radiation induces a dipole in matter by redistributing its electron density. Tuning the frequency of EM radiation to match the natural frequency of matter results in significant dipole oscillations. In the weak field limit, the amplitude of the electric field is small and so is the probability of transitions. (1) In the strong-field limit of light–matter interactions, excitation with a high-intensity classical EM field results in a significant population in the upper level and the coherent superposition of states. In this limit, an atom can oscillate between two levels at the Rabi angular frequency, ΩR. This oscillatory behavior of an atom in the presence of a strong field is called Rabi flopping or Rabi oscillation. (1) In contrast, deexcitation from the upper level takes place faster than ΩR in the weak field regime.
The quantum description presents the EM field as an infinite set of harmonic oscillators, where every radiation mode has an oscillator. In its ground state, all of the oscillators have a residual energy of ℏω/2 resulting from the zero-point (quantum) fluctuations, often known as the vacuum EM field, even though it is a zero-photon state. (2) The cavity quantum electrodynamics (QED) opens up new possibilities of using the vacuum EM field to obtain the Rabi oscillations instead of a strong external light field. The incident photon in a Fabry–Pérot cavity can bounce back and forth inside in phase, confining the EM field within the cavity boundary to generate the resonances with a much larger field amplitude than nonresonant frequencies. (2−4) The cavity can be tuned to the natural frequency of matter, resulting in an ultrafast exchange of virtual photons between the cavity and matter, giving rise to Rabi oscillations. (2,5) Here, the Rabi oscillations originate from the vacuum EM field instead of an intense classical EM field. (5) The reversible matter–EM vacuum interaction results in light–matter strong coupling, where in the matter transitions hybridize with the cavity mode, forming the hybrid light–matter states, or in other words, a mixed state of light and matter, known as the polaritonic states. (2,3)
In the early experiments, physicists focused on using high-quality cavities to strongly couple Rydberg atoms and semiconductor quantum wells at low temperature. (5,6) Interestingly, the introduction of molecules into the cavity (7) opened a plethora of emergent molecular properties from the collective interaction of molecular transition dipoles and cavity modes. (3,4) The initial experiments in molecular strong coupling were about achieving the light–matter hybridization using different molecules and various photonic architectures. (7−10) However, considerable interest toward the strong coupling of organic molecules started with the seminal experiments by the Ebbesen group in 2012. (11,12) Not only did they achieve ultrastrong coupling of the merocyanine electronic transition (electronic strong coupling or ESC) using a resonant Fabry–Pérot cavity but also a slowdown of the spiropyran to merocyanin photoisomerization. (11) The latter laid the foundation for polaritonic chemistry. (12,13) Since then, multiple groups have shown modifications to the photoisomerization of different molecular systems under ESC, including reproducing the original spiropyran/merocyanine results. (14−16) A recent ellipsometry-based experiment (17) did not find a change in the photoisomerization rate upon excitation of the polaritonic states of merocyanine. However, the latter investigation (17) is different from the original experiment, (11) as commented on by Hutchison et al. (18) Interestingly, Lee et al. showed that the photoisomerization pathways in merocyanine can be steered through polariton-assisted funneling of the absorbed energy toward a target reactant state by appropriately tuning the cavity resonances. (16) These studies showed that the photoisomerization reactions can be controlled through light–matter strong coupling, and more experiments can lead to a better understanding of the excited-state reactivity under ESC.
Later on, the experiments were extended from ESC to vibrational strong coupling (VSC), where a vibrational transition of the molecule or the material is strongly coupled to the cavity mode. (19,20) Subsequent observation of modified chemistry under VSC (20,21) generated great excitement among chemists, and a library of chemical reactions has been studied under VSC since then. (12,13) However, two reports (22,23) raised reproducibility concerns about the results of Lather et al. (24) and Hiura et al. (25) Interestingly, recent experiments (26) in an open cavity have shown 2.7 times enhanced reactivity for the same reaction as that studied in ref (24). Lian et al. (27) showed an order of magnitude enhancement for the solvolysis of 4-nitrophenyl octoanoate, a reactant similar to 4-nitrophenyl acetate, which was investigated by Lather et al. (24) In another study, Wang et al. (28) showed that VSC modifies the kinetics of one of the experiments reported in ref (25). It shows that the experimental parameters are critical to realizing the modified kinetics under VSC. The growing interest toward polaritonic chemistry over the past decade has pushed the boundaries to achieve strong coupling from a single molecule (29) to an ensemble of molecules by confining the light field ranging from Fabry–Pérot cavities (11,20) to hole arrays (10) to the newly introduced metasurfaces. (26) Several research groups have focused on understanding different chemical processes such as energy transfer, (30−32) charge transfer, (33−35) and chemical reactivity. (12,13) However, the theoretical description of chemistry modifications, especially under VSC, has been challenging. (36−39) Questions such as whether the modification in energetics is solely responsible for the observed changes or the altered molecular interactions play a crucial role, remain open. Although polaritonic chemistry is in its infancy, it still provides a compelling new approach to understanding molecular-level chemistry in detail. This Spotlight on Applications presents how modified intermolecular interactions under light–matter strong coupling can impact polariton-mediated transport and chemistry.

2. Formation of Polaritonic States under Light–Matter Strong Coupling

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One of the most interesting implications of QED is disrupting the view of spontaneous emission as the intrinsic property of matter. (2) It describes the spontaneous emission as a stimulation of matter–vacuum coupling, where the emitted photon resides on one of the infinite continuums of vacuum states (Figure 1A). A Fabry–Pérot cavity made of a pair of highly reflecting mirrors (such as Au, Ag, Al, etc.) separated by a medium of thickness and refractive index is one of the simplest devices to confine the photons (Figure 1B) compared to other photonic architectures. (1) The cavity resonances (Figure 1C) provide a unique opportunity to enhance or suppress spontaneous emission through engineering the density and availability of the vacuum states. (2) The strong coupling of electronic or vibrational transitions of molecules occurs due to the ultrafast exchange of energy between the molecular transition and the cavity upon achieving the resonance condition, resulting in the formation of polaritonic states (P+ and P–). These polaritonic states are separated by the Rabi splitting energy (ℏΩR) corresponding to the EM vacuum field–matter coupling strength. In the absence of dissipation, this picture of the strong interaction of a single cavity quantized EM field with a two-level molecule can be explained through the Jaynes–Cummings model, as shown by eq 1. (40)
H=H0+V=Hm+Hc+V=12ℏωmσz+ℏωca†a+ℏg0(aσ++a†σ−)
(1)
where σ+, σ–, and σz are the raising, lowering, and inversion operators and a and a† are the photon annihilation and creation operators, respectively. ωm and ωc correspond to the molecular transition and cavity mode frequency, and g0 signifies the coupling strength. The absorption of a photon leads to excitation of the molecule to its excited state and subsequent annihilation of a photon from the cavity mode, described by aσ+. On the other hand, a†σ– corresponds to the emission of a photon from the molecule and subsequent photon creation inside the cavity. Therefore, the Hamiltonian couples |e,n⟩ and |g,n+1⟩ , where n is the number of photons inside the cavity. Interestingly, even without an external photon, the Jaynes–Cummings model still produces two new eigenstates (P+ and P–) due to the matter–EM vacuum interaction, separated by vacuum Rabi splitting energy (as shown by eqs 2–4). This model can be extended to the interaction between more than one molecule and a single cavity mode through a more realistic model deduced by Tavis and Cummings. (41) It considers N quantum oscillators collectively interacting with the resonant cavity mode with a coupling strength of g0√N. When there are no external photons inside the cavity, the Jaynes–Cummings Hamiltonian couples the |e,0⟩ and |g,1⟩ states with coefficients α and β (Figure 1D). The vacuum Rabi splitting depends on the number of molecules (N), the volume of the EM mode (V), and the transition-dipole moment of the molecules (d).

Figure 1

Figure 1. (A) Two-level atomic system with quantized energy levels emitting a photon into a continuum of vacuum states. (B) Schematic illustration of a Fabry–Pérot cavity with its resonances. (C) FT-IR transmission spectrum showing the resonances of a Fabry–Perot cavity of 8 μm path length filled with air. Schematic representation of (D) the energy exchange between a lossless cavity and a molecule resulting in the Rabi oscillation and (E) the resulting strong coupling and formation of the light–matter hybrid states in a cavity. (F) Angle-dependent dispersion of the polaritonic states with respect to the in-plane wave vector (black diamonds) overlaid on the simulated dispersion contour of the uncoupled cavity mode (ℏωc = 698 cm–1) and the vibrational transition of PS (ℏωm = 698 cm–1). Adapted from ref (34). Copyright 2024 American Chemical Society.

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|P+⟩=α|e,0⟩+β|g,1⟩
(2)
|P−⟩=β|e,0⟩−α|g,1⟩
(3)
Rabisplittingenergy=ℏΩR=2ℏgNn+1=2dNℏωc2ϵ0Vn+1
(4)
The formation of polaritonic states can be monitored by absorption spectroscopic techniques such as UV–vis (for ESC) and Fourier transform infrared (FT-IR) spectroscopy (for VSC). The polaritonic states appear as two new peaks in the spectrum, while molecular absorption disappears. However, only observing split peaks in the transmission spectra does not always certify strong coupling. The split peaks can also originate from a strong molecular transition (or strong absorber) interacting with a lossy cavity resonance (i.e., self-induced transparency) and remain in the weak matter–vacuum coupling regime. The coupling strength depends on the rate of photon exchange, which can be tuned by controlling the cavity mode volume (V) and the number of oscillators (N) present inside the cavity. Achieving a different regime of light–matter coupling depends on three parameters: the matter–vacuum coupling rate (gN), the photon decay rate of the cavity (κ), and the decay rate of matter (γ). The light–matter interaction remains in the weak coupling regime when gN ≪ (κ, γ). However, in this regime, the irreversible and resonant interaction of the cavity with the matter transition modifies the rate of spontaneous emission, which goes beyond the weak field limit of Einstein’s theory of spontaneous emission. On the other hand, the strong coupling regime is achieved by increasing the matter–vacuum coupling when gN ≫ (κ, γ), resulting in two hybrid light–matter polaritonic states.
Globally, researchers have employed different conditions of strong coupling (Figure 1E) by including the damping parameters, resulting in the modified conditions, i.e., gN2 > (γ – κ)2/4 or gN2 > (γ2 + κ2)/2. The onset of these conditions can be interpreted as strong coupling even without splitting energy levels. So, explaining the experimental results using such conditions may result in dubious data interpretation. Therefore, it is better to consider the strong coupling regime only when the vacuum Rabi splitting energy (ℏΩR), which directly corresponds to gN, becomes independently larger ℏΩR ≫ (κ, γ) than the full width at half-maximum (fwhm) of molecular absorption (Δωm ≈ τm–1 ≈ γ) and the fwhm of the cavity resonance (Δωc ≈ τcav–1 ≈ κ). The cavity resonance disperses with respect to the in-plane momentum of light (k||; k|| = 2πλsin⁡θ). Therefore, the angle-dependent dispersion measurements (E vs k||), where we probe the absorption of polaritonic states by tuning the angle of light incidence (θ), are necessary to verify the strong coupling condition (Figure 1F). The dispersion of polaritonic states indicates the mixing of photonic characteristics with the molecule. The Rabi splitting must be calculated at the point of resonance. In our polaritonic chemistry experiments, (34,42,43) we prepare the cavity mode in resonance with the molecular transition energy at k|| = 0. So, we determine the strong coupling by probing the normal incidence of light (θ = 0) to determine the Rabi splitting.
The delocalized nature of the collective polaritonic states enthused researchers to explore the transport properties of molecules under light–matter strong coupling. It included experiments to understand whether the polaritonic emission has an extended coherence and whether energy and charge transport are improved under strong coupling. In the later sections, we present an overview of such experimental results.

3. Energy Transport under Strong Coupling

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Excitonic coupling between the chromophores in the light-harvesting antenna of the bacterocholorophyls plays a crucial role in the efficient energy transfer in photosynthetic systems. (44) Since a cavity mode can couple to the donor and acceptor transitions, exploring whether light–matter strong coupling can enhance the energy transfer was natural. Interestingly, strong coupling of the donor (D) and acceptor (A) transitions with a single cavity mode results in an enhanced energy transfer (30,31) through the upper (UP), middle (MP), and lower (LP) polaritonic states (Figure 2A). The UP and LP states are the admixtures of donor–photon and acceptor–photon. (30) However, MP was truly a donor–photon–acceptor admix. Interestingly, MP acts as a bridge that quickly funnels the excitation energy of UP to the LP state, significantly enhancing the energy-transfer rate and efficiency. The LP population rises concomitantly with the MP decay, signifying the bridging role of MP (Figure 2B). What is even more remarkable is that the resonance energy transfer goes beyond the Förster limit (≤10 nm) and becomes independent of the spatial separation (10–100 nm) between D and A when strong coupling is preserved (Figure 2C). (31) It shows that the cavity mode can effectively connect the energy transfer between the donor and acceptor even if they are spatially separated. The transient absorption measurements probing the decay kinetics of the MP state show that its lifetime remains invariant to physical separation of the chromophores (Figure 2D). (31) The Förster theory explains the excitation energy-transfer process by invoking the quantum mechanical coupling between the chromophores through dipole–dipole interactions. (44) It necessitates properly oriented transition dipoles of the donor and acceptor (orientation factor, κ2) and spectral overlap to provide the resonance condition. Recent theoretical studies demonstrate the critical role of the MP state in enabling the vibrations to take excitation energy from the UP state to the LP state, independent of the D and A arrangement and the physical separation, as long as the collective strong coupling is maintained. (45) These results demonstrate that the excitation energy transfer under strong coupling can no longer be explained only through the Förster resonance energy-transfer model.

Figure 2

Figure 2. (A) Schematic representation of strong coupling of the electronic transitions of the donor and acceptor, together with a cavity resonance, resulting in three polaritonic states: the upper polariton (UP), middle polariton (MP), and lower polariton (LP). Reproduced from ref (30). Copyright 2016 John Wiley and Sons. (B) Excited-state dynamics of MP and LP. Adapted from ref (30). Copyright 2016 John Wiley and Sons. (C) Schematic representation of a cavity containing spatially separated donors and acceptors. The spatial separation corresponds to the thickness (h) of the polymer layer. Reproduced from ref (31). Copyright 2017 John Wiley and Sons. (D) Lifetime of MP as a function of the spacer thickness in the strong coupling conditions. Adapted from ref (31). Copyright 2017 John Wiley and Sons. (E) Momentum-resolved ultrafast imaging of pure exciton transport (top panel) and polariton transport (bottom panel). Reproduced from ref (48). Available under a CC-BY 4.0 license. Copyright 2023 Xu et al. (F) Time-resolved dynamics of the variance of polariton cloud expansion measured at different photonic fractions showing the ballistic and diffusive energy transport mediated by polaritons. Adapted from ref (47). Copyright 2023 Springer Nature.

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The coherent emission from molecules over a micrometer-length separation under ESC showed that the energy propagation under strong coupling could overcome the molecular disorder. (46) Recent experiments have probed the propagation of polaritons through a momentum-resolved pump–probe imaging technique, showcasing the light-like energy flow. (47,48) The polariton propagation reaches the ballistic regime at a higher photonic fraction (Figure 2E,F). As the excitonic fraction increases, the exciton–polariton–phonon interaction renormalizes it back to a diffusive regime. (48) Interestingly, even with a substantial excitonic fraction, the propagation remains coherent, exhibiting a 6 orders of magnitude larger diffusion coefficient than the uncoupled molecules. (47−49) Thus, light–matter strong coupling introduces a new regime of donor–acceptor dipole coupling and provides a physical handle to tune the coupling between different quantum states.

4. Charge Transport under Strong Coupling

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The intermolecular interactions play a crucial role in charge-transport processes, such as ionic or electrical conductivity. For instance, the charge distribution of a molecule can be altered when it starts to interact with another molecule or an EM field. That is why the acidity of a molecule varies from the ground state to the excited state, leading to an efficient proton transfer in the excited state compared to its ground state. Interestingly, the ionic conductivity of the H+, Li+, Na+, K+, Rb+, and Cs+ ions under VSC of the −OH stretching vibrational modes of water is enhanced by an order of magnitude depending on the ionic radii (Figure 3A). (50,51) An increase in the dielectric constant of the medium suggests that the light–matter strong coupling effectively modifies the ion–solvent interactions. Such an enhancement in the ionic conductance and a change in the dielectric constant are possible if there is an enhanced nuclear coherence and correlation between the water molecules. (50) In this direction, we probed the proton-transfer process upon photoexcitation, i.e., excited-state proton transfer (ESPT) through cooperative VSC of the O–H stretching vibration of 7-hydroxy-1-naphthalenesulfonate (N8S) with a host matrix [poly(vinyl alcohol), PVA]. Herein, we observed that the cooperative VSC of the O–H stretching vibration of N8S doubles the rate of the ESPT process (Figure 3B). (43) Our results also indicate that the collective strong coupling facilitates enhanced proton transfer from one site to another, (47) through the PVA matrix, pointing toward VSC controlling the intermolecular interactions.

Figure 3

Figure 3. (A) Schematic representation of the ionic conductivity under VSC of the O–H stretching vibrational mode of water. Adapted from ref (50). Copyright 2022 American Chemical Society. (B) Emission intensity ratio IRO–/IROH, as a function of the different cavity tunings. The blue spheres indicate the emission ratio in different cavities with resonances at the wavenumbers noted on the x axis. The purple dotted curve shows absorption of the PVA −OH stretching mode. The black dashed line indicates the average IRO–/IROH observed in noncavities. Adapted from ref (43). Copyright 2025 John Wiley and Sons. (C) I–V plot of the PDI2EH-CN2 deposited on hexagonal hole arrays with different periods of holes. Reproduced from ref (10). Copyright 2015 Springer Nature. (D) Schematic representation of a mirrorless MOSFET Fabry–Pérot cavity. The blue curve shows the cavity mode interacting with the active layer. (E) Electron mobility as a function of the cavity tuning. The first- and second-mode cavities are prepared by tuning the thickness of the organic semiconductor. The bottom panel shows the cavity mode position with respect to the electronic transition of the semiconductor (D and E) Adapted from ref (53). Copyright 2021 John Wiley and Sons.

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Besides the mobility of ions, strong light–matter coupling has greatly impacted the electrical conductivity through molecules. In a seminal report, Orgiu et al. showed that the electrical conductivity of PDI2EH-CN2, an organic semiconductor, can be enhanced by an order of magnitude under strong coupling of its electronic transition with the surface plasmon modes of hole arrays (Figure 3C). (10) Interestingly, a similar semiconductor molecule with a Br substitution (PDI2EH-Br2) instead of CN did not show any enhancement. Charge transport can be strongly inhibited by molecular disorder, independent of the transport mechanism. Although PDI2EH-Br2 has a molecular architecture similar to PDI2EH-CN2, it has much lower mobility due to the disorder. The authors found negligible enhancement in conductivity despite the strong coupling. The P(NDI2OD-T2) polymer presents an intermediate case where, despite the lower conductivity, the latter is enhanced by strong coupling. Considering their similarity in structure, the orientation of molecules can vary drastically by modification from Br2 to CN2 to bithiophene (T2). Due to the planar geometry of the CN2 and T2 groups, PDI2EH-CN2 and P(NDI2OD-T2) can undergo π–π stacking. The variation in the crystal packing motifs of the PDIs is attributed to the intramolecular nonbonded repulsions and the torsional distortions in the PDI core. (52) While the unsubstituted PDI core remains planar, the substitution forces an increased torsional angle of 5.2° for PDI-CN2 to 24° for PDI-Br2. Further, such a core substitution also gives rise to a significant change in the intermolecular spacing. Dicyano to dibromo substitution increases the interplanar spacing from 3.4 to 3.64 Å. These crystal structure alterations through substitutions in the PDI core indicate that a large core twisting originates due to halogenation inhibiting the π–π interactions. (52) On the contrary, significantly less distortion occurs by the relatively small cyano groups, which keep the molecular geometry planar and facilitate π–π interactions. This indicates that the nature of the intermolecular interactions plays a critical role in the enhanced conductivity under ESC. In a later experiment, Kaur et al. used mirrorless MOSFET cavities to show the enhancement in the conductivity for PDI2EH-CN2. (53) The mirrorless cavity has a lower quality factor, and the mobility is enhanced by 3 times. The resonant light–matter interaction is achieved by tuning the layer thickness of PDI2EH-CN2 (Figure 3D). Although the lowest thickness of PDI2EH-CN2 (8 nm) is too low to reach the strong coupling, a leaky cavity mode still shows an improved carrier mobility (top panel of Figure 3E). Further, under strong coupling with the second mode of the cavity, an enhanced carrier mobility is observed, scaling with cavity tuning (middle panel of Figure 3E). Contemporary theoretical studies that include ESC of a 1D chain of a quantum system having dipole–dipole interaction show an enhanced exciton transport through the delocalized polaritonic states. (54) Transport can even circumvent the disordered media to reach from one end to the other, opening up a new conducting pathway over the molecule’s own conduction path, as further observed experimentally in the case of organic and inorganic conductors. (55)
Interestingly, VSC has an even more remarkable impact on the conductivity of disordered polymer systems. In a serendipitous measurement, we observed a conductivity of 9 S m–1 for polystyrene (PS), under VSC of its aromatic C–H out-of-plane bending, δ(Ar. CH), modes, which is otherwise an insulator under noncavity conditions. (34) The observation is further confirmed by probing the conductance of the cavity in resonance with δ(Ar. CD) modes of deuterated polystyrene (PS-d8). The C–D vibrational modes of PS-d8 are red-shifted compared to the PS vibrational modes (Figure 4A,B). Interestingly, VSC of δ(Ar. CD) modes resulted in 6-order enhanced conductance, confirming the extraordinary enhancement in conductance under VSC. To better understand the effect of strong coupling strength on the conductance, we performed the conductance measurement by varying the Rabi splitting energy of the PS 698 cm–1 δ(Ar. CH) mode, as shown in Figure 4A. The gradual change in conductance with the Rabi splitting energy signifies the importance of coupling strength to achieve improved transport through these amorphous polymers (Figure 4C). Further, the cavities are carefully tuned in and out of resonance with other vibrations of PS and PS-d8 to obtain deeper knowledge of the role of different molecular vibrations. A similar conductance is observed for VSC of non-δ(Ar. CH) modes as off-resonance cavities, indicating their noninvolvement in producing the enhanced transport. (34) In contrast, the aliphatic polymer poly(methyl methacrylate) (PMMA) has no modes supporting the vibronic coupling and remains as an insulator inside the cavity (Figure 4D). So, the conductance observed for off-resonance and VSC of non-δ(Ar. CH) modes arises due to the surface plasmon strongly coupling with the δ(Ar. CH) modes.

Figure 4

Figure 4. (A) FT-IR transmission spectra of cavities strongly coupled to the δ(Ar. CH) modes of PS when mixed with different weight percents of PS-d8. (B) Schematic illustration of VSC resulting in polaritonic states and the electrical conductance measurement setup. (C) Variation in conductance as a function of the strong coupling strength. (D) Action spectra of the electrical conductivity of aromatic polymers (PS and PS-d8) and nonaromatic polymer (PMMA) inside the cavity. The cavity modes are tuned with respect to the different vibrations of the polymers. The red, blue, and pink spheres correspond to the current densities of PS, PS-d8, and PMMA, respectively. Adapted from ref (34). Copyright 2024 American Chemical Society.

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The conductance measurement shows temperature-independent transport under VSC of δ(Ar. CH(D)) modes of polymers as long as VSC is maintained, indicating that the nature of interaction between the monomer units in the polymer could be varied under VSC. (34) Our qualitative transport model suggests that the cavity-induced enhanced conductivity is due to the connection between the electronic orbitals of PS, which is achieved through δ(Ar. CH) phonons dressed by the cavity, leading to the reduction in the activation barrier. Further, the transport remains independent of the thickness of the polymer layers as long as the strong coupling condition is maintained. These observations show that the electron–phonon coupling and delocalized polaritonic states under collective strong coupling overcome micrometer-scale molecular disorders, as seen in experiments on the superconductivity and ferromagnetism under VSC. (12) The experimental and theoretical studies on energy and charge transport indicate that the short-range intermolecular coupling can be tuned by the arrangement of the species in proximity. The collective strong coupling can expand the short-range effect into the long-range effect by delocalizing the polaritonic states across all of the molecules.

5. Ground-State Intermolecular Interactions under Strong Coupling

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The emergent properties discussed above can be thought of as arising from changes in the intermolecular interactions. These interactions, which include H-bonding, electrostatic, and van der Waals interactions, etc., (56) can take place not only between the solute molecules but also among the solvent and solute–solvent molecules. However, the interesting question is whether light–matter strong coupling can modify the intermolecular interactions. VSC experiments have shown that ground-state molecular interactions can be altered, leading to changes in crystallization (57) and self-assembly. (58−60) For instance, poly(p-phenyleneethynylene) (PPE), under VSC, self-assembles to form flake-like structures compared to fiber-like morphology in noncavity conditions (Figure 5A). (58) The kinetics of the PPE self-assembly are also modified under the cooperative VSC. Hirai et al. achieved accelerated selective crystallization of ZIF-8 under VSC of the O–H stretching vibration of water, compared to the formation of ZIF-8 and ZIF-L polymorphs in noncavity conditions.

Figure 5

Figure 5. (A) Schematic representation of a Fabry–Pérot cavity containing PPE dissolved in dichlorobenzene. The cooperative VSC transforms the morphology of the polymer from fiber to sheets. Adapted from ref (58). Copyright 2021 John Wiley and Sons. (B) Supramolecular polymerization of chiral zinc porphyrin under on- and off-resonance conditions probed through electronic circular dichroism (ECD). The ECD signals of these cavities are plotted with respect to different temperatures as a function of the concentration. The elongation temperature of S–Zn is denoted by the yellow dashed line. Adapted from ref (59). Available under a CC-BY 4.0 license. Copyright 2025 Joseph et al. (C) Schematic illustration showing transformation of the naphthalenediimide supramolecular polymer in response to the click reaction under VSC and noncavity situations and their atomic force microscopy images. Adapted from ref (60). Available under a CC-BY 4.0 license. Copyright 2025 Imai et al.

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Recent experiments show that supramolecular polymerization, a dynamic polymerization technique driven by noncovalent interactions, can be modified by VSC. Joseph et al. showed that the cooperative VSC limits the stabilization of polymer chain elongation at a critical temperature (Figure 5B). (59) The elongation temperature of the supramolecular polymer reduces in the resonance condition compared to the noncavity and off-resonance cavity. Imai et al. utilized the cooperative strong coupling (VSC of the −CH stretching vibration) to show the morphological evolution of a supramolecular polymer. (60) An interesting aspect of the finding is that only the supramolecular polymer showed an enhanced transformation under VSC, while the monomer alone did not show any alteration in the kinetics. This suggests that VSC impacts the assembly more than the individual molecule reaction. The simulations showed a weakened alkyl interaction under VSC with slipped packing. These changes to the supramolecular polymer under VSC yield a toroidal structure, in contrast to the thick-fiber architecture under normal conditions (Figure 5C). (60) These experimental observations that are probed through optical and nonoptical observables demonstrate the role of VSC in modifying the dispersion forces (61) involved in solute–solute, solvent–solvent, and solute–solvent interactions, therefore, the intermolecular interactions.
Now, the question is whether VSC alone shows the changes in the intermolecular interactions or if ESC can also alter molecular interactions. Interestingly, the thermodynamic properties (62) and work function (63) of molecules show changes under ESC. Additionally, most experiments showing modifications in the transport properties are under ESC conditions. (10,47,48,53,54) Recent theoretical investigations also predict changes to the noncovalent interactions by tuning the polarizability of the solvent shell to drive molecular aggregation and chemical reactivity under ESC. (64,65) On the contrary, foreseeing an impact on the ground-state property through ESC is unusual and rarely explored.
In this direction, we provided the experimental realization of modified ground-state intermolecular interactions under ESC by following the spectral characteristics of Chlorin e6 trimethyl ester (Ce6T). (42) The Ce6T molecules in a thin-film state maintain their characteristic Soret and Q bands and in addition show a new weak absorption band at 727 nm. Such an absorption band signifies favorable preorganization and assembly of molecules through weak intermolecular interactions. This weak excitonic coupling band emerges from coupling and delocalization of the molecular transition dipoles. Interestingly, the Ce6T films show an intense red-shifted emission at 740 nm compared with regular molecular emission at 674 nm in solution. From the detailed analysis of excitation spectra and time-resolved fluorescence decay, we conclude that the 740 nm emission corresponds to the excimer-like emission (42) and the 674 nm emission belongs to the monomer emission. Hence, Ce6T offers exclusivity in investigating the role of ESC (by coupling the Soret and Q bands) in checking whether excitonic coupling in Ce6T remains the same (Figure 6A).

Figure 6

Figure 6. (A–C) Transmittance, emission (λex = 450 nm), and excitation (for λem = 770 nm) spectra of cavities ranging from weak (purple curves) to strong (red curves) coupling of the Ce6T Q band. (D and E) Transmittance, emission, and excitation (for λem = 770 nm) spectra of the Ce6T thin film and cavity strongly coupled to the Soret band. (F) Schematic illustration of the excimer-like exciton formation between two interacting Ce6T molecules in a noncavity film upon spin coating (top panel). The bottom panel shows the Ce6T molecules with a suppressed intermolecular interaction under ESC. Reproduced from ref (42). Available under a CC BY-NC-ND 4.0 license. Copyright 2025 Biswas et al.

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Interestingly, the photophysical characteristics of on- and off-resonance cavities are significantly different. The on-resonance cavity showed significant suppression of excimer-like emission and an intense polaritonic emission; in contrast, the off-resonance cavity followed an emission feature similar to that of the noncavity Ce6T thin films (Figure 6B). Strikingly, the excitation spectral analysis reveals the absence of the excitonic coupling band, indicating the absence of excitonic coupling band formation under ESC (Figure 6C). The modification of emission and excitation spectral characteristics is clearly visible as we transform from a weak coupling regime to a strong coupling regime (Figure 6B). This remarkable phase-transition-like change in the photophysical character from weak to strong coupling also indicates the changes in the molecular interactions. Further, the lifetime of the 740 nm emission band under ESC is similar to the lifetime of the noncavity monomer emission suggesting its dark state (monomer-like) nature. This can arise from the rearrangement of polaritonic states and the dark states based on their difference in free energies. (66) The lower entropy of polaritonic states moves them above the dark states and facilitates significant population transfer from polaritonic states to the dark states. (42,66) To further generalize our observed modification, we focused on the Soret band. Placing the λ/2 mode in resonance with the Soret band opens a wavelength window that does not alter the optical environment around the Ce6T emission (Figure 6D). Interestingly, we observe an intense, sharp monomer emission with a suppressed red-shifted emission under strong coupling with the subsequent disappearance of the excitonic coupling band from the excitation spectrum (Figure 6E). All of our experimental signatures indicate that ESC modifies the ground-state intermolecular interactions to prevent excitonic coupling band formation, which otherwise exists in the noncavity conditions (Figure 6F). Therefore, the changes in the polymer self-assembly, (58) crystallization, (57) supramolecular polymerization, (58−60) work function, (63) and Ce6T self-assembly (42) point toward the modification of weak intermolecular forces in driving the chemical reactivity and photophysical characteristics under the collective strong coupling of molecular transitions, be it electronic or vibrational, with the quantized EM field.

6. Conclusions and Outlook

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In summary, we have discussed how resonant light–matter interactions change from free space to the cavity by invoking quantum light. Quantization of the EM field through photonic devices, such as a Fabry–Pérot cavity, tunes the density and availability of the vacuum states. In this Spotlight on Applications, we have detailed the studies on strong light–matter coupling in modifying the optical and transport properties of molecules. Because the bulk molecular properties are governed by the intermolecular interactions between the molecular units, we try to emphasize that collective light–matter strong coupling must also modify these interactions to show the altered properties. The emergent properties appear through changes in the steady-state kinetics, morphology, emission characteristics, and charge transport. A right molecular system is important in light–matter strong coupling experiments. In our conductivity experiments, as we mentioned in ref (34), the use of PS to optimize our experiments was fortuitous; however, it was not a random selection because we wanted a polymer that fulfills vibronic coupling requisites. On the contrary, if we had started our experiments with another polymer (PMMA), then we would have found that VSC is ineffective in changing its conductivity (Figure 4D) because PMMA does not contain the right vibrational mode facilitating the conductivity modification. (34) Once a proper system is identified, it is also important to generalize the results using molecular systems of a similar class. This can reveal if any molecular structure property relationship exists in strong coupling experiments, as we saw in the case of polymer conductivity. (34) Similarly, the recent phenomenological approach based on molecular symmetry qualitatively explains and predicts changes in reactivity under VSC for a larger set of molecules. (33,35) It must be noted that symmetry correlations dictate the vibronic coupling, chemical reactivity, (67) etc., in molecular systems. Interestingly, the symmetry of polaritonic states can be different from the molecular symmetry in the noncavity and, therefore, can control the molecular interactions. It can also affect the vibrational energy flow and properties arising from it. (39,68,69) Thus, in our view, the molecular structure property relationship is critical in strong coupling. In this aspect, it is worth noting that, in the work of Imai et al., only the reactivity of the supramolecular polymer is modified. (60) In contrast, the reaction kinetics of the monomer are not affected, showing a clear structure–property relationship under strong coupling experiments. So, the emphasis on looking at changes in the reaction kinetics alone may not always reveal the impact of strong coupling. To achieve predictability in light–matter strong coupling experiments, especially in the collective regime, performing more experiments and generalizing the results are important. Again, we note that the emergent properties in the collective strong coupling regime can differ from those seen at the single-molecule level, and the light–matter strong coupling could be more effective in modifying intermolecular interactions. The recent development in using the spin-glass theory to explain the polaritonic effects also emphasizes the collective interaction of the molecules under strong coupling. (70) Thus, we believe that plenty of fundamental and applied aspects are still to be explored under collective molecular light–matter strong coupling because most applications of molecules and materials are in the bulk and not at the individual level. Additional experiments and theory can help us understand all of the possibilities of controlling the intermolecular interactions under strong coupling and unlock novel avenues.

Author Information

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Acknowledgments

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S.B. thanks DST-INSPIRE and the Prime Minister’s Research Fellowship for a Ph.D. fellowship. A.T. is thankful for a IISc start-up grant and a SERB-CRG grant (CRG/2021/002396) for funding. We thank Harsh Baliyan and Kavya S. Mony for their discussion and inputs.

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  • Abstract

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    Figure 1

    Figure 1. (A) Two-level atomic system with quantized energy levels emitting a photon into a continuum of vacuum states. (B) Schematic illustration of a Fabry–Pérot cavity with its resonances. (C) FT-IR transmission spectrum showing the resonances of a Fabry–Perot cavity of 8 μm path length filled with air. Schematic representation of (D) the energy exchange between a lossless cavity and a molecule resulting in the Rabi oscillation and (E) the resulting strong coupling and formation of the light–matter hybrid states in a cavity. (F) Angle-dependent dispersion of the polaritonic states with respect to the in-plane wave vector (black diamonds) overlaid on the simulated dispersion contour of the uncoupled cavity mode (ℏωc = 698 cm–1) and the vibrational transition of PS (ℏωm = 698 cm–1). Adapted from ref (34). Copyright 2024 American Chemical Society.

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    Figure 2

    Figure 2. (A) Schematic representation of strong coupling of the electronic transitions of the donor and acceptor, together with a cavity resonance, resulting in three polaritonic states: the upper polariton (UP), middle polariton (MP), and lower polariton (LP). Reproduced from ref (30). Copyright 2016 John Wiley and Sons. (B) Excited-state dynamics of MP and LP. Adapted from ref (30). Copyright 2016 John Wiley and Sons. (C) Schematic representation of a cavity containing spatially separated donors and acceptors. The spatial separation corresponds to the thickness (h) of the polymer layer. Reproduced from ref (31). Copyright 2017 John Wiley and Sons. (D) Lifetime of MP as a function of the spacer thickness in the strong coupling conditions. Adapted from ref (31). Copyright 2017 John Wiley and Sons. (E) Momentum-resolved ultrafast imaging of pure exciton transport (top panel) and polariton transport (bottom panel). Reproduced from ref (48). Available under a CC-BY 4.0 license. Copyright 2023 Xu et al. (F) Time-resolved dynamics of the variance of polariton cloud expansion measured at different photonic fractions showing the ballistic and diffusive energy transport mediated by polaritons. Adapted from ref (47). Copyright 2023 Springer Nature.

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    Figure 3

    Figure 3. (A) Schematic representation of the ionic conductivity under VSC of the O–H stretching vibrational mode of water. Adapted from ref (50). Copyright 2022 American Chemical Society. (B) Emission intensity ratio IRO–/IROH, as a function of the different cavity tunings. The blue spheres indicate the emission ratio in different cavities with resonances at the wavenumbers noted on the x axis. The purple dotted curve shows absorption of the PVA −OH stretching mode. The black dashed line indicates the average IRO–/IROH observed in noncavities. Adapted from ref (43). Copyright 2025 John Wiley and Sons. (C) I–V plot of the PDI2EH-CN2 deposited on hexagonal hole arrays with different periods of holes. Reproduced from ref (10). Copyright 2015 Springer Nature. (D) Schematic representation of a mirrorless MOSFET Fabry–Pérot cavity. The blue curve shows the cavity mode interacting with the active layer. (E) Electron mobility as a function of the cavity tuning. The first- and second-mode cavities are prepared by tuning the thickness of the organic semiconductor. The bottom panel shows the cavity mode position with respect to the electronic transition of the semiconductor (D and E) Adapted from ref (53). Copyright 2021 John Wiley and Sons.

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    Figure 4

    Figure 4. (A) FT-IR transmission spectra of cavities strongly coupled to the δ(Ar. CH) modes of PS when mixed with different weight percents of PS-d8. (B) Schematic illustration of VSC resulting in polaritonic states and the electrical conductance measurement setup. (C) Variation in conductance as a function of the strong coupling strength. (D) Action spectra of the electrical conductivity of aromatic polymers (PS and PS-d8) and nonaromatic polymer (PMMA) inside the cavity. The cavity modes are tuned with respect to the different vibrations of the polymers. The red, blue, and pink spheres correspond to the current densities of PS, PS-d8, and PMMA, respectively. Adapted from ref (34). Copyright 2024 American Chemical Society.

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    Figure 5

    Figure 5. (A) Schematic representation of a Fabry–Pérot cavity containing PPE dissolved in dichlorobenzene. The cooperative VSC transforms the morphology of the polymer from fiber to sheets. Adapted from ref (58). Copyright 2021 John Wiley and Sons. (B) Supramolecular polymerization of chiral zinc porphyrin under on- and off-resonance conditions probed through electronic circular dichroism (ECD). The ECD signals of these cavities are plotted with respect to different temperatures as a function of the concentration. The elongation temperature of S–Zn is denoted by the yellow dashed line. Adapted from ref (59). Available under a CC-BY 4.0 license. Copyright 2025 Joseph et al. (C) Schematic illustration showing transformation of the naphthalenediimide supramolecular polymer in response to the click reaction under VSC and noncavity situations and their atomic force microscopy images. Adapted from ref (60). Available under a CC-BY 4.0 license. Copyright 2025 Imai et al.

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    Figure 6

    Figure 6. (A–C) Transmittance, emission (λex = 450 nm), and excitation (for λem = 770 nm) spectra of cavities ranging from weak (purple curves) to strong (red curves) coupling of the Ce6T Q band. (D and E) Transmittance, emission, and excitation (for λem = 770 nm) spectra of the Ce6T thin film and cavity strongly coupled to the Soret band. (F) Schematic illustration of the excimer-like exciton formation between two interacting Ce6T molecules in a noncavity film upon spin coating (top panel). The bottom panel shows the Ce6T molecules with a suppressed intermolecular interaction under ESC. Reproduced from ref (42). Available under a CC BY-NC-ND 4.0 license. Copyright 2025 Biswas et al.

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