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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Continuum model of strong light-matter coupling for molecular polaritons

Strong coupling between light and matter generates hybrid polariton modes. We present a continuum formalism that expresses the polariton modes in terms of light and matter densities of states (DOS). We derive exact expressions for the light and matter DOS for a planar cavity containing a strongly dispersive dielectric.We show that these DOS depend exclusively on the linear response of the cavity components, i.e., the reflectance of the mirrors and the susceptibility of the dielectric. Here, we further show that, within the strong coupling regime, the light and matter DOS are well approximated by coupled mode theory. Altogether, our continuum formalism offers a unified treatment of polaritons that connects the framework of light-matter coupling with that of linear dispersion.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Diffusion quantum Monte Carlo approach to the polaritonic ground state

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent and active fields that connects the communities of chemistry and quantum optics. Modeling of such polaritonic phenomena using ab initio approaches calls for new methodologies, leading to the reinvention of many commonly used electronic structure methods, such as Hartree-Fock, density functional, and coupled cluster theories. Here in this work, we explore the formally exact diffusion quantum Monte Carlo approach to obtain numerical solutions to the polaritonic ground state during the dissociation of the H 2 molecular system. Here, we examine various electron-nuclear-photon properties throughout the dissociation, such as changes to the minimum of the cavity Born-Oppenheimer surface, the localization of the electronic wave function, and the average mode occupation. Finally, we directly compare our results to that obtained with state-of-the-art, yet approximate, polaritonic coupled cluster approaches.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Linear response of molecular polaritons

In this article, we show that the collective light–matter strong coupling regime where N molecular emitters couple to the photon mode of an optical cavity can be mapped to a quantum impurity model where the photon is the impurity that is coupled to a bath of anharmonic transitions. In the thermodynamic limit where N ≫ 1, we argue that the bath can be replaced with an effective harmonic bath, leading to a dramatic simplification of the problem into one of the coupled harmonic oscillators. We derive simple analytical expressions for linear optical spectra (transmission, reflection, and absorption) where the only molecular input required is the molecular linear susceptibility. This formalism is applied to a series of illustrative examples, showing the role of temperature, disorder, vibronic coupling, and optical saturation of the molecular ensemble, explaining that it is useful even when describing an important class of nonlinear optical experiments. For completeness, we provide Appendixes A–C that include a self-contained derivation of the relevant spectroscopic observables for arbitrary anharmonic systems (for both large and small N) within the rotating-wave approximation. While some of the presented results herein have already been reported in the literature, we provide a unified presentation of the results as well as new interpretations that connect powerful concepts in open quantum systems and linear response theory with molecular polaritonics.

Chemistry↗
DOE OSTI2023

Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling

Polariton chemistry may provide a new means to control molecular reactivity, permitting remote, reversible modification of reaction energetics, kinetics, and product yields. A considerable body of experimental and theoretical work has already demonstrated that strong coupling between a molecular vibrational mode and the confined electromagnetic field of an optical cavity can alter chemical reactivity without external illumination. However, the mechanisms underlying cavity-altered chemistry remain unclear in large part because the experimental systems examined previously are too complex for detailed analysis of their reaction dynamics. Here, we experimentally investigate photolysis-induced reactions of cyanide radicals with strongly-coupled chloroform (CHCl 3 ) solvent molecules and examine the intracavity rates of photofragment recombination, solvent complexation, and hydrogen abstraction. Here we use a microfluidic optical cavity fitted with dichroic mirrors to facilitate vibrational strong coupling (VSC) of the C–H stretching mode of CHCl 3 while simultaneously permitting optical access at visible wavelengths. Ultrafast transient absorption experiments performed with cavities tuned on- and off-resonance reveal that VSC of the CHCl 3 C–H stretching transition does not significantly modify any measured rate constants, including those associated with the hydrogen abstraction reaction. This work represents, to the best of our knowledge, the first experimental study of an elementary bimolecular reaction under VSC. We discuss how the conspicuous absence of cavity-altered effects in this system may provide insights into the mechanisms of modified ground state reactivity under VSC and help bridge the divide between experimental results and theoretical predictions in vibrational polariton chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Polariton spectra under the collective coupling regime. I. Efficient simulation of linear spectra and quantum dynamics

We outline two general theoretical techniques to simulate polariton quantum dynamics and optical spectra under the collective coupling regimes described by a Holstein–Tavis–Cummings (HTC) model Hamiltonian. The first one takes advantage of sparsity of the HTC Hamiltonian, which allows one to reduce the cost of acting polariton Hamiltonian onto a state vector to the linear order of the number of states, instead of the quadratic order. The second one is applying the well-known Chebyshev series expansion approach for quantum dynamics propagation and to simulate the polariton dynamics in the HTC system; this approach allows us to use a much larger time step for propagation and only requires a few recursive operations of the polariton Hamiltonian acting on state vectors. These two theoretical approaches are general and can be applied to any trajectory-based non-adiabatic quantum dynamics methods. We apply these two techniques with our previously developed Lindblad-partially linearized density matrix approach to simulate the linear absorption spectra of the HTC model system, with both inhomogeneous site energy disorders and dipolar orientational disorders. Our numerical results agree well with the previous analytic and numerical work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Controlling magnon-photon coupling in a planar geometry

Abstract The tunability of magnons enables their interaction with various other quantum excitations, including photons, paving the route for novel hybrid quantum systems. Here, we study magnon-photon coupling using a high-quality factor split-ring resonator and single-crystal yttrium iron garnet (YIG) sphere at room temperature. We investigate the dependence of the coupling strength on the size of the sphere and find that the coupling is stronger for spheres with a larger diameter as predicted by theory. Furthermore, we demonstrate strong magnon-photon coupling by varying the position of the YIG sphere within the resonator. Our experimental results reveal the expected correlation between the coupling strength and the rf magnetic field. These findings demonstrate the control of coherent magnon-photon coupling through the theoretically predicted square-root dependence on the spin density in the ferromagnetic medium and the magnetic dipolar interaction in a planar resonator.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Trapping light in air with membrane metasurfaces for vibrational strong coupling

Optical metasurfaces can manipulate electromagnetic waves in unprecedented ways at ultra-thin engineered interfaces. Specifically, in the mid-infrared (mid-IR) region, metasurfaces have enabled numerous biochemical sensing, spectroscopy, and vibrational strong coupling (VSC) applications via enhanced light-matter interactions in resonant cavities. However, mid-IR metasurfaces are usually fabricated on solid supporting substrates, which degrade resonance quality factors (Q) and hinder efficient sample access to the near-field electromagnetic hotspots. Besides, typical IR-transparent substrate materials with low refractive indices, such as CaF 2 , NaCl, KBr, and ZnSe, are usually either water-soluble, expensive, or not compatible with low-cost mass manufacturing processes. Here, we present novel free-standing Si-membrane mid-IR metasurfaces with strong light-trapping capabilities in accessible air voids. We employ the Brillouin zone folding technique to excite tunable, high-Q quasi-bound states in the continuum (qBIC) resonances with our highest measured Q-factor of 722. Leveraging the strong field localizations in accessible air cavities, we demonstrate VSC with multiple quantities of PMMA molecules and the qBIC modes at various detuning frequencies. Our new approach of fabricating mid-IR metasurfaces into semiconductor membranes enables scalable manufacturing of mid-IR photonic devices and provides exciting opportunities for quantum-coherent light-matter interactions, biochemical sensing, and polaritonic chemistry. The authors introduce a mid-IR metasurface fabricated by decorating a free-standing Si-membrane with air holes. The enhanced light-matter interactions in such air cavities enable vibrational strong coupling and advanced biochemical sensing.

infrared spectroscopy↗
DOE OSTI2022

Polariton Dynamics in Two-Dimensional Ruddlesden–Popper Perovskites Strongly Coupled with Plasmonic Lattices

Strong coupling between light and matter can produce hybrid eigenstates known as exciton-polaritons. Although polariton dynamics are important photophysical properties, the relaxation pathways of polaritons in different coupling regimes have seen limited attention. This paper reports the dynamics of hybridized states from 2D Ruddlesden-Popper perovskites coupled to plasmonic nanoparticle lattices. The open cavity architecture of Al lattices enables the coupling strength to be modulated by varying either the lead halide perovskite film thickness or the superstrate refractive index. Both experiments and finite-difference time-domain simulations of the optical dispersion diagrams showed avoided crossings that are a signature of strong coupling. Furthermore, our analytical model also elucidated the correlation between the exciton/plasmon mixing ratio and polariton coupling strength. Using fs-transient absorption spectroscopy, we found that both the upper and lower polaritons have shorter lifetimes than the excitons and that polaritons can show faster excited state dynamics when they have access to additional energy transfer channels.

2D perovskite↗
DOE OSTI2024

Polariton-assisted incoherent to coherent excitation energy transfer between colloidal nanocrystal quantum dots

Here, we explore the dynamics of energy transfer between two nanocrystal quantum dots placed within an optical microcavity. By adjusting the coupling strength between the cavity photon mode and the quantum dots, we have the capacity to fine-tune the effective coupling between the donor and acceptor. Introducing a non-adiabatic parameter, γ, governed by the coupling to the cavity mode, we demonstrate the system’s capability to shift from the overdamped Förster regime (γ $\ll$ 1) to an underdamped coherent regime (γ $\gg$ 1). In the latter regime, characterized by swift energy transfer rates, the dynamics are influenced by decoherence time. To illustrate this, we study the exciton energy transfer dynamics between two closely positioned CdSe/CdS core/shell quantum dots with sizes and separations relevant to experimental conditions. Employing an atomistic approach, we calculate the excitonic level arrangement, exciton–phonon interactions, and transition dipole moments of the quantum dots within the microcavity. These parameters are then utilized to define a model Hamiltonian. Subsequently, we apply a generalized non-Markovian quantum Redfield equation to delineate the dynamics within the polaritonic framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molecular and solid-state topological polaritons induced by population imbalance

Abstract Strong coupling between electronic excitations in materials and photon modes results in the formation of polaritons, which display larger nonlinearities than their photonic counterparts due to their material component. We theoretically investigate how to optically control the topological properties of molecular and solid-state exciton–polariton systems by exploiting one such nonlinearity: saturation of electronic transitions. We demonstrate modification of the Berry curvature of three different materials when placed within a Fabry–Perot cavity and pumped with circularly polarized light, illustrating the broad applicability of our scheme. Importantly, while optical pumping leads to nonzero Chern invariants, unidirectional edge states do not emerge in our system as the bulk-boundary correspondence is not applicable. This work demonstrates a versatile approach to control topological properties of novel optoelectronic materials.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Gate-Tunable Single Terahertz Meta-Atom Ultrastrong Light-Matter Coupling

We study the electrical tunability of ultrastrong light-matter interactions between a single terahertz circuit-based complementary split ring resonator (cSRR) and a two-dimensional electron gas. For this purpose, transmission spectroscopy measurements are performed under the influence of a strong magnetic field at different set points for the electric gate bias. The resulting Landau polariton dispersion depends on the applied electric bias, as the gating technique confines the electrons in-plane down to extremely subwavelength dimensions as small as d = 410 nm. This confinement allows for the excitation of standing plasma waves at zero magnetic field and an effective tunability of the electron number coupled to the THz resonator. This allows the normalized coupling strength to be tuned in situ from η = 0.46 down to η = 0.18. This is the first demonstration of terahertz far-field spectroscopy of an electrically tunable interaction between a single terahertz resonator and electrons in a GaAs quantum well heterostructure.

Landau levels↗
DOE OSTI2022

Molecular polariton electroabsorption

Abstract We investigate electroabsorption (EA) in organic semiconductor microcavities to understand whether strong light-matter coupling non-trivially alters their nonlinear optical [ $${\chi }^{(3)}\left(\omega,{{{{\mathrm{0,0}}}}}\right)$$ χ ( 3 ) ω , 0, 0 ] response. Focusing on strongly-absorbing squaraine (SQ) molecules dispersed in a wide-gap host matrix, we find that classical transfer matrix modeling accurately captures the EA response of low concentration SQ microcavities with a vacuum Rabi splitting of $$\hslash \Omega \approx 200$$ ℏ Ω ≈ 200 meV, but fails for high concentration cavities with $$\hslash \Omega \approx 420$$ ℏ Ω ≈ 420 meV. Rather than new physics in the ultrastrong coupling regime, however, we attribute the discrepancy at high SQ concentration to a nearly dark H-aggregate state below the SQ exciton transition, which goes undetected in the optical constant dispersion on which the transfer matrix model is based, but nonetheless interacts with and enhances the EA response of the lower polariton mode. These results indicate that strong coupling can be used to manipulate EA (and presumably other optical nonlinearities) from organic microcavities by controlling the energy of polariton modes relative to other states in the system, but it does not alter the intrinsic optical nonlinearity of the organic semiconductor inside the cavity.

42 ENGINEERING↗
DOE OSTI2023

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Most photochemistry occurs in the regime of weak light–matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light–matter interactions between an optical field and multiple molecules lead to collective hybrid light–matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. Here, the effect of strong light–matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light–matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.

Cavities↗
DOE OSTI2026

Scalable Quantum Monte Carlo Method for Polariton Chemistry via Mixed Block Sparsity and Tensor Hypercontraction Method

We present a reduced-scaling auxiliary-field quantum Monte Carlo (AFQMC) framework designed for large molecular systems and ensembles, with or without coupling to optical cavities. Our approach leverages the natural block sparsity of the Cholesky decomposition (CD) of electron repulsion integrals in molecular ensembles and employs tensor hypercontraction (THC) to efficiently compress low-rank Cholesky blocks. By representing the Cholesky vectors in a mixed format, keeping high-rank blocks in block-sparse form and compressing low-rank blocks with THC, we reduce the scaling of exchange-energy evaluation from quartic to robust cubic in the number of molecular orbitals N, while lowering memory from cubic toward quadratic. Benchmark analyses on one-, two-, and three-dimensional molecular ensembles (up to ∼1,200 orbitals) show that (a) the number of nonzeros in Cholesky tensors grows linearly with system size across dimensions; (b) the average numerical rank increases sublinearly and does not saturate at these sizes; and (c) rank heterogeneity─some blocks nearly full rank and many low rank, naturally motivates the proposed mixed block sparsity and THC scheme for efficient calculation of exchange energy. In conclusion, we demonstrate that the mixed scheme yields cubic wall-time scaling with favorable prefactors and preserves AFQMC accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Quantum nondemolition photon counting with a hybrid electromechanical probe

Quantum nondemolition (QND) measurements of photons is a much pursued endeavor in the field of quantum optics and quantum information processing. Here, we propose a hybrid optoelectromechanical platform that integrates a cavity system with a hybrid electromechanical probe for QND photon counting. Building upon a mechanical-mode-mediated nonperturbative electro-optical dispersive coupling, our protocol performs the QND photon counting measurement by means of the current-voltage characteristics of the probe. In particular, we show that the peak voltage shift of the differential conductance is linearly dependent on the photon occupation number, thus providing a sensitive measure of the photon number, especially in the strong optomechanical coupling regime. Here, given that our proposed hybrid system is compatible with state-of-the-art experimental techniques, we discuss its implementations and anticipate applications in quantum optics and polariton physics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory

The description of strongly correlated systems interacting with quantized cavity modes poses significant theoretical challenges due to the combinatorial scaling of electronic and photonic degrees of freedom. Recent advances addressing this complexity include cavity quantum electrodynamics (QED) generalizations of complete active space configuration interaction and density matrix renormalization group methods. In this work, we introduce a QED extension of state-averaged complete active space self-consistent field theory, which incorporates cavity-induced correlations through a second-order orbital optimization framework with robust convergence properties. The method is implemented using both photon number state and coherent state representations, with the latter showing robust origin invariance in the energies regardless of the completeness of the photonic Fock space. The implementation enables symmetry-free orbital relaxations to account for photon-mediated symmetry breaking in polaritonic systems. Numerical validation on lithium hydride, hydroxide anion, and magnesium hydride cation demonstrates that this method achieves significantly improved accuracy in modeling ground-state and polariton potential energy surfaces compared to QED-CASCI in a fixed orbital basis. In these studies, we reach sub-kcal/mol accuracy in potential energy surface in much smaller active spaces than are required for QED-CASCI. This advancement provides a more robust approach for studying cavity-altered chemical landscapes for ground and exited strongly coupled systems.

CASSCF↗
DOE OSTI2025

Thermally tunable mid-infrared nanocavity resonance of coupled surface plasmon-phonon polaritons

Phase-change materials (PCMs) are essential for achieving tunability of metasurfaces. However, they frequently face limitations in the long-wave infrared range because of their lossy behavior. Here, we experimentally demonstrate a thermally tunable mid-infrared nanocavity resonance from coupled surface plasmon-phonon polaritons that are supported within a trilayer structure of metal-PCM layer-polar dielectric (Au-VO 2 -SiC). The top metal structures configure the Fabry-Perot cavity resonance near 840 cm −1 (11.9 µm), which is sensitively tunable and reversible with small changes in the VO 2 refractive index ∆n near below its insulator-to-metal phase transition temperature where the loss is small. The maximum resonance shift of 7.7 cm −1 is induced by a small ∆n = 0.3 over a temperature change of 3°C. The tuning figure of merit is comparable to the current standard in photonic modulator applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Polaritonic Bright and Dark States Collectively Affect the Reactivity of a Hydrolysis Reaction

Vibrational strong coupling (VSC) has emerged as a means for modifying chemical reactivity. Despite the intriguing discoveries and progresses in the field, the precise mechanisms that govern polaritonic chemistry still deserve further interrogation. Herein, we use the hydrolysis of ammonia borane in D 2 O as an exemplary reaction and systematically investigate the influence of VSC on its reactivity. Experimental evidence of the coexistence of a resonant effect and reaction acceleration is observed in this system. In particular, we find that when the O-D stretching mode of D 2 O is strongly coupled to a cavity mode, reaction acceleration is observed. The reaction rate acceleration factor, mu, is consistently observed to be dependent on the coupling conditions between the vibrational and cavity modes, and reaches a minimum at zero mode detuning, suggesting that a resonant effect is likely in play. In addition, we find that mu decreases with an increasing Rabi splitting. Based on these experimental findings, we propose that the overall influence of VSC on this reaction is likely determined collectively by the polaritonic bright and dark states. In conclusion, these findings could help shed new light on the intricate effects of VSC on ground-state reaction landscapes.

Rabi splitting↗