arXiv subjects

Joel Yuen-Zhou

Publications and source records attributed to Joel Yuen-Zhou.

At least 19 recordsLinked to original sources

arXiv2026

Full-wave nonlinear microscopy reveals guided channel for ultrafast polariton transport

We show how finite-difference time-domain (FDTD) simulations can be extended to model ultrafast nonlinear microscopy, enabling the prediction of spatially-resolved pump--probe signals in arbitrary electromagnetic environments. Focusing on polariton transport in strongly coupled light--matter systems, we develop a perturbative framework to study the ultrafast propagation of hybrid light--matter excitations in nanophotonic structures. We first apply the framework to a standard distributed Bragg reflector (DBR) cavity, reproducing established results for polariton transport from a multimode Tavis--Cummings model. We then consider the full modal landscape of the same cavity, including guided modes below the light line that are typically neglected in single-mode-family descriptions. Exploiting these modes, we design compact mode converters that transfer radiative cavity polaritons into photon-like guided polaritons and back, utilizing the guided modes for low-loss propagation. Despite molecular dephasing, this enables transport of molecular excitation over a millimeter, an order of magnitude beyond current transport experiments. We further compute the pump--probe differential transmission signal, providing an experimental signature of the mechanism. Our results show that the modal landscape of a photonic cavity can be engineered to bypass limitations commonly assumed to be intrinsic to the transport of molecular polaritons.

quant-ph↗

arXiv2026

Hidden optical nonlinearities in linear spectra of quantum emitter arrays

Classical optical frameworks such as the discrete dipole approximation (DDA) assume that the linear spectrum of coupled quantum emitters can be computed solely from the linear susceptibilities of individual constituents. However, recent polariton studies show that cavity linear response can encode nonlinear optical susceptibilities. Here, we demonstrate that this phenomenon is more general: emitter-emitter interactions allow nonlinearities of individual emitters to emerge in the linear response of arrays, without cavities or permutational symmetry. To illustrate this phenomenon, we show linear spectra for coupled heterodimers and linear chains, and demonstrate that Raman features of individual monomers show up as vibrational sidebands of collective resonances. Moreover, tuning Raman-type anharmonicities enables systematic control of spectral features, establishing a genuine quantum optical effect in molecular aggregates and quantum emitter arrays, which goes beyond mean-field descriptions in light-matter interactions.

physics.optics↗

arXiv2026

Multidimensional semiclassical single- and double-quantum spectroscopy of anharmonic molecular polaritons

We present a general and efficient approach to compute phase-resolved multidimensional spectra of anharmonic molecular polaritons, based on a semiclassical evolution of the molecular Hamiltonian and cavity field in the large-$\mathcal{N}$ limit of many molecules coupled to a confined photonic mode. By systematically expanding the response in both amplitudes and phases of the input fields, our method enables a transparent and computationally simple construction of phase-cycled two-dimensional single- and double-quantum polariton spectra from the underlying nonlinear signal components. Here, phase cycling acts as an analogue of phase matching with oblique pulses, allowing for the isolation of the contributing nonlinear pathways in Liouville space. We specialize to vibrational polaritons and benchmark the method through direct comparison with experimentally measured single-quantum spectra, providing an explanation for the longstanding puzzle of the polariton bleach effect observed at short waiting times. Further, we show how the imprint of various types of anharmonicities on the double-excitation manifold can be directly probed and analyzed through double-quantum coherence spectroscopy. Taken together, our results establish a practical and powerful framework for the modeling and interpretation of nonlinear spectroscopic experiments on strongly coupled light-matter platforms and for guiding the design of cavity-enhanced molecular platforms.

quant-ph↗

arXiv2026

Permutationally symmetric molecular aggregates

Linear optical spectra of molecular aggregates are often approximated by classical optics methods such as the discrete-dipole approximation (DDA), coherent exciton scattering (CES), and coherent potential approximation (CPA), where the only quantum-mechanical input to the calculation is the linear susceptibility of the monomers. However, the limits of validity of these classical optics methods remain opaque. Here, starting from a quantum mechanical Hamiltonian for the aggregate, we identify a limit where DDA/CPA/CES is exact: all-to-all coupled permutationally symmetric aggregates of $N \to \infty$ monomers. The permutational symmetry of this molecular version of the Lipkin-Meshkov-Glick model, which is closely related to that of the molecular polariton problem of many identical molecules coupled to a single-cavity mode, allows us to borrow recent techniques developed for the latter. In particular, we identify a $1/N$ expansion that corrects the classical optics limit with finite $N$ corrections to the linear response of the aggregate. These corrections feature as Raman-like transitions of a single monomer. We illustrate these findings with calculations on the very physically-relevant setup of a homodimer. Our findings clarify how quantum optical features that go beyond classical optics can already be present in simple arrays of quantum emitters such as molecular aggregates.

quant-ph↗

arXiv2026

Dynamical Drexhage Effect: Amplified Emission in Time-Modulated Electromagnetic Environments

We investigate the effect of nonrelativistic motion on the emission dynamics of a dipole emitter moving next to a reflecting interface. Within the formalism of macroscopic QED, we obtain a general equation of motion for the dipole amplitude in terms of the dyadic Green's function, yielding a dynamical extension of the Drexhage effect. At short dipole-surface distances, the dipole can be described as a parametric oscillator featuring time-dependent dampings and Lamb shifts, both arising from the self-induced modulation of the surrounding electromagnetic environment. Importantly, these time-dependent parameters do not always average out, leading to amplification of the dipole amplitude and the radiated intensity when considering certain sinusoidal trajectories with specific modulation amplitudes and frequencies. We derive threshold modulation amplitudes as function of the relative permittivities at the interface. Qualitatively, in the vicinity of certain epsilon-near-zero materials, amplification is possible purely by modulation of the damping. Our findings open up avenues for the dynamic control of light-matter interaction in nanophotonic environments.

physics.optics↗

arXiv2025

Towards coherent polaritonic circuits operating at room temperature

Polariton condensation is a potential system state for performing analog computations, given that it exhibits quantum behavior at macroscopic scales readily probed with low-cost optical methods. Current methods of fabricating devices in polariton microcavities largely involve patterning the devices via e-beam lithography before the cavity is completed, which offers less flexibility in device creation and reduces the maximum possible refractive index contrast. Moreover, the momentum and spatial distributions of the condensate are highly dependent on the host platform, and it has been difficult to preserve the desired behavior when modifying a given cavity. Here we introduce a method that addresses both of these challenges with the creation of polaritonic circuits of arbitrary forms etched via Focused Ion Beam into an organic microcavity based on Rhodamine 3B Perchlorate within a Small Molecule Ionic Isolation Lattices complex. We demonstrate room temperature condensation and propagation of polaritons in rectangular and trapezoidal waveguides by analyzing spatial and angle-resolved photoluminescence. We also discuss the blue-shifting and non-zero momentum of the condensate and show that it is strongly confined up to several higher energy levels. As an example, we report the spatial profiles of condensation in custom devices, such as a ring waveguide, a Y-splitter, and a Mach-Zehnder interferometer. This work represents a first step towards the realization of more complex, fully integrated, coherent polaritonic circuits operating at room temperature.

physics.optics↗

arXiv2025

High-Q microresonators unveil quantum rare events

Classical linear optics posits that at sufficiently low intensities, light propagation in dielectric media is governed solely by their linear susceptibilities. Here, we demonstrate a departure from this paradigm in high-Q microresonators, where prolonged photon confinement enables rare quantum electrodynamical (QED) events, mediated by the quantum vacuum, to embed distinctive Raman signatures of the coupled analyte into the resonator's linear transmission spectrum despite their absence from the linear susceptibility. We further show that increasing the amount of adsorbed analyte amplifies these Raman fingerprints well above typical noise floors, rendering them experimentally accessible with state-of-the-art photonic architectures and detection schemes. This novel weak-coupling cavity-QED effect offers unique routes to harness extended photon lifetimes and constrained geometries for leveraging vacuum fluctuations in next-generation photonic technologies for chemical and biological sensing and high-precision optical spectroscopy.

physics.optics↗

arXiv2025

When do molecular polaritons behave like optical filters?

This review outlines several linear optical effects featured by molecular polaritons arising in the collective strong light-matter coupling regime. Under weak laser irradiation and when the single-molecule light-matter coupling can be neglected (often in the limit when the number of molecules per photon mode is large), we show that the excited-state molecular dynamics under collective strong coupling can be exactly replicated without the cavity using a shaped (or ``filtered'') laser, whose field amplitude is enhanced by the cavity quality factor, shining on the bare molecules. As a consequence, the absorption within a cavity can be understood as the overlap between the polariton transmission and the bare molecular absorption, suggesting that polaritons act in part as optical filters. This framework demystifies and provides a straightforward explanation for a large class of experiments and theoretical models in molecular polaritonics, highlighting that the same effects can be achieved without the cavity with shaped laser pulses. With a few modifications, this simple conceptual picture can also be adapted to understand the incoherent nonlinear response of polaritonic systems. This review establishes a clear distinction between polaritonic phenomena that can be fully explained through classical linear optics and those that require a quantum electrodynamics approach. It also highlights the need to differentiate between effects that necessitate polaritons (i.e., hybrid light-matter states) and those that can occur in the weak coupling regime. We further discuss that certain quantum optical effects like fluorescence can be partially described as optical filtering, whereas some others like cavity-induced Raman scattering go beyond this. Further exploration in these areas is needed to uncover novel polaritonic phenomena beyond optical filtering.

physics.chem-ph↗

arXiv2025

Exploring the Delocalization of Dark States in a Multimode Optical Cavity

The strong coupling between molecules and photonic modes in a Fabry-Pérot optical cavity, which forms hybrid light-matter states called polaritons, has been demonstrated as a promising route to control the rates of chemical reactions. However, theoretical studies, which largely employ models with a single cavity mode, cannot explain the experimentally observed kinetic changes. While simplified multimode models with one spatial dimension can capture experimental features involving the polariton states, it is unclear whether they can also describe the dark states. Here, we study the delocalization of dark states for molecules in a multimode cavity, accounting for the three-dimensional nature of experimental setups. Accounting for energetic and orientational disorder, but fixing Rabi splitting and intermolecular distances (i.e., no positional disorder), we find that the delocalization of the dark states scales linearly with the number of molecules in the plane parallel to the cavity mirrors, in contrast to one-dimensional multimode models. Adding layers of molecules along the axis normal to the mirrors increases the delocalization much less. Similar to the one-dimensional models, the dark-state delocalization is enhanced for smaller values of molecular energetic disorder, relative to the light-matter coupling, and cavities with longer longitudinal length. Our work indicates that for certain phenomena, understanding the dark states under strong light-matter coupling might require a proper multimode description of the optical cavity.

quant-ph↗

arXiv2025

Nonlinear semiclassical spectroscopy of ultrafast molecular polariton dynamics

We introduce a theoretical framework that allows for the systematic and efficient description of the ultrafast nonlinear response of molecular polaritons, i.e., hybrid light-matter states, in the collective regime of large numbers of molecules $\mathcal N$ coupled to the cavity photon mode. Our approach is based on a semiclassical, mean-field evolution of the molecular Hamiltonian and the cavity field, which is complemented by a perturbative expansion of both light and matter counterparts in the input fields entering the cavity. In addition, expansion in terms of the pulse phases enables us to disentangle different excitation pathways in Liouville space, thereby distinguishing contributions to the nonlinear response. The formalism extends traditional free-space nonlinear spectroscopy by incorporating the feedback of matter onto the light field via the induced polarization. We demonstrate the utility of the framework by applying it to the calculation of pump-probe polariton spectra and show how, by storing the pulses, the cavity facilitates additional excitation pathways, which can be used to isolate purely bright state contributions. Our method, which does not scale with $\mathcal N$, is broadly applicable and can be extended to model a wide range of current experiments investigating the dynamical nonlinear response of hybrid light-matter states.

quant-ph↗

arXiv2025

Mapping molecular polariton transport via pump-probe microscopy

We demonstrate how the transport properties of molecular polaritons in optical cavities can be extracted from a microscopic modeling of pump-probe spectroscopy. Our approach combines a mean-field treatment of the light-matter Hamiltonian with a perturbative expansion of both light and matter components, along with spatial coarse-graining. This approach extends semiclassical cavity spectroscopy to multimode light-matter interactions, providing full access to spatially resolved transient spectra. By simulating a microscopy experiment with counter-propagating pump and probe pulses, we compute the differential transmission and show how molecular dephasing and persistent dark exciton populations drive sub-group-velocity transport of the root-mean-square displacement. We analyze transport across the polariton dispersion, showing how velocity renormalization correlates with excitonic weight, consistent with experimental observations, and further its dependence on the rate of molecular dephasing. Our results highlight the need to consider measured spectroscopic observables when characterizing transport in polaritonic systems.

quant-ph↗

arXiv2025

Radiative pumping vs vibrational relaxation of molecular polaritons: a bosonic mapping approach

We present a formalism to study molecular polaritons based on the bosonization of molecular vibronic states. This formalism accommodates an arbitrary number of molecules $N$, excitations and internal vibronic structures, making it ideal for investigating molecular polariton processes accounting for finite $N$ effects. We employ this formalism to rigorously derive radiative pumping and vibrational relaxation rates. We show that radiative pumping is the emission from incoherent excitons and divide its rate into transmitted and re-absorbed components. On the other hand, the vibrational relaxation rate in the weak linear vibronic coupling regime is composed of a $\mathcal{O}(1/N)$ contribution already accounted for by radiative pumping, and a $\mathcal{O}(1/N^2)$ contribution from a second-order process in the \textit{single}-molecule light-matter coupling that we call polariton-assisted Raman scattering. This scattering is enhanced when the difference between fluorescence and lower polariton frequencies matches a Raman-active excitation.

quant-ph↗

arXiv2025

Quantum theory of surface lattice resonances

The collective interactions of nanoparticles arranged in periodic structures give rise to high-$Q$ in-plane diffractive modes known as surface lattice resonances. While these resonances and their broader implications have been extensively studied within the framework of classical electrodynamics and linear response theory, a quantum optical theory capable of describing the dynamics of these structures, especially in the presence of material nonlinearities beyond \textit{ad hoc} few-mode approximations, is largely missing. To this end, we consider a lattice of metallic nanoparticles coupled to the electromagnetic field and derive the quantum input--output relations within the electric dipole approximation. As applications, we analyze coupling between the nanoparticle array and external quantum emitters, and show how the formalism extends to molecular optomechanics, where the high $Q$-factors of SLRs enable coupling to collective vibrational modes. We further consider arrays composed of saturable excitonic emitters, demonstrating how emitter nonlinearities can be used to switch the SLR condition between electronic transitions. Using a perturbative approach that accounts for population dynamics, we show how these effects can be probed in pump--probe experiments and give rise to nonlinear phase-matching phenomena. Our work provides a microscopic framework for modeling SLRs interacting with quantum emitters without phenomenological descriptions of the electromagnetic environment.

quant-ph↗

arXiv2024

Enhancing the ODMR Signal of Organic Molecular Qubits

In quantum information science and sensing, electron spins are often purified into a specific polarisation through an optical-spin interface, a process known as optically-detected magnetic resonance (ODMR). Diamond-NV centres and transition metals are both excellent platforms for these so-called colour centres, while metal-free molecular analogues are also gaining popularity for their extended polarisation lifetimes, milder environmental impacts, and reduced costs. In our earlier attempt at designing such organic high-spin $π$-diradicals, we proposed to spin-polarise by shelving triplet $M_{S}=\pm1$ populations as singlets. This was recently verified by experiments albeit with low ODMR contrasts of $<1\%$ at temperatures above 5 K. In this work, we propose to improve the ODMR signal by moving singlet populations back into the triplet $M_{S}=0$ sublevel, designing a true carbon-based molecular analogue to the NV centre. Our proposal is based upon transition-orbital and group-theoretical analyses of beyond-nearest-neighbour spin-orbit couplings, which are further confirmed by ab initio calculations of a realistic trityl-based radical dimer. Microkinetic analyses point towards high ODMR contrasts of around $30\%$ under experimentally-feasible conditions, a stark improvement from previous works. Finally, in our quest towards ground-state optically-addressable molecular spin qubits, we exemplify how our symmetry-based design avoids Zeeman-induced singlet-triplet mixings, setting the scene for realising electron spin qubit gates.

physics.chem-ph↗

arXiv2024

Hidden nonlinear optical susceptibilities in linear polaritonic spectra

Linear spectra of molecular polaritons formed by $N$ molecules coupled to a microcavity photon mode are usually well described by classical linear optics, raising the question of where the expected nonlinear effects in these strongly coupled systems are. In this work, we derive a general expression for the polaritonic linear spectra that reveal previously overlooked finite-size quantum corrections due to vacuum-mediated molecular Raman processes. Using a $1/N$ expansion, we demonstrate that these nonlinearities are suppressed in typical low-Q cavities due to an emergent timescale separation in polariton dynamics yet manifest in high-Q single-mode cavities where the photon loss is comparable to the single-molecule light-matter coupling strength.

quant-ph↗

arXiv2024

CUT-E as a $1/N$ expansion for multiscale molecular polariton dynamics

Molecular polaritons arise when the collective coupling between an ensemble of $N$ molecules and an optical mode exceeds individual photon and molecular linewidths. The complexity of their description stems from their multiscale nature, where the local dynamics on each molecule can, in principle, be influenced by the collective behavior of the entire ensemble. To address this, we previously introduced a formalism called collective dynamics using truncated equations (CUT-E). CUT-E approaches the problem in two stages. First, it exploits permutational symmetries to obtain a substantial simplification of the problem. However, this is often insufficient for parameter regimes relevant to most experiments. Second, it takes the exact solution of the problem in the $N\to\infty$ limit as a reference and derives systematic $\mathcal{O}(1/N)$ corrections. Here we provide a novel derivation of CUT-E based on recently developed bosonization techniques. We lay down its connections with $1/N$ expansions that are ubiquitous in other fields of physics, and present previously unexplored key aspects of this formalism, including various types of approximations and extensions to high excitation manifolds.

quant-ph↗

arXiv2024

Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder

We present a powerful formalism, disordered collective dynamics using truncated equations (d-CUT-E), to simulate the ultrafast quantum dynamics of molecular polaritons in the collective strong coupling regime, where a disordered ensemble of $N\gg10^{6}$ molecules couples to a cavity mode. Notably, we can capture this dynamics with a cavity hosting a single \textit{effective} molecule with $\sim N_{bins}$ electronic states, where $N_{bins}\ll N$ is the number of bins discretizing the disorder distribution. Using d-CUT-E we conclude that strong coupling, as evaluated from linear optical spectra, can be a poor proxy for polariton chemistry. For highly disordered ensembles, total reaction yield upon broadband excitation is identical to that outside of the cavity, while narrowband excitation produces distinct reaction yields solely due to differences in the initial states prepared prior to the reaction.

quant-ph↗

arXiv2024

Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition metal complexes via optically-detected magnetic resonance (ODMR) mechanisms analogous to the diamond-NV colour centre. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts. At present, most luminescent open-shell organic molecules are $π$-diradicals, but such systems often suffer from poor ground-state open-shell characters necessary to realise a stable ground-state molecular qubit. In this work, we use alternancy symmetry to selectively minimise radical-radical interactions in the ground state, generating $π$-systems with high diradical characters. We call them m-dimers, referencing the need to covalently link two benzylic radicals at their meta carbon atoms for the desired symmetry. Through a detailed electronic structure analysis, we find that the excited states of alternant hydrocarbon m-diradicals contain important symmetries that can be used to construct ODMR mechanisms leading to ground-state spin polarisation. The molecular parameters are set in the context of a tris(2,4,6-trichlorophenyl)methyl (TTM) radical dimer covalently tethered at the meta position, demonstrating the feasibility of alternant m-diradicals as molecular colour centres.

physics.chem-ph↗