Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 9786 - 9879

Published: Aug. 8, 2023

When molecules are coupled to an optical cavity, new light-matter hybrid states, so-called polaritons, formed due quantum interactions. With the experimental demonstrations of modifying chemical reactivities by forming polaritons under strong interactions, theorists have been encouraged develop methods simulate these systems and discover strategies tune control reactions. This review summarizes some exciting theoretical advances in polariton chemistry, ranging from fundamental framework computational techniques applications spanning photochemistry vibrational coupling. Even though theory interactions goes back midtwentieth century, gaps knowledge molecular electrodynamics (QED) only recently filled. We recent made resolving gauge ambiguities, correct form different QED Hamiltonians gauges, their connections various optics models. Then, we developed ab initio approaches which can accurately describe states a realistic molecule-cavity system. then discuss using method advancements. advancements where cavity is resonant electronic transitions nonadiabatic excited state dynamics enable photochemical reactivities. resonance tuned vibrations instead, ground-state reaction modifications demonstrated experimentally, its mechanistic principle remains unclear. present progress this mystery. Finally, understanding collective coupling regime between light matter, many collectively couple single mode or modes. also lay out current challenges explain observed results. hope that will serve as useful document for anyone who wants become familiar with context chemistry thus significantly benefit entire community.

Language: Английский

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From enhanced diffusion to ultrafast ballistic motion of hybrid light–matter excitations

Nature Materials, Journal Year: 2023, Volume and Issue: 22(3), P. 338 - 344

Published: Jan. 16, 2023

Language: Английский

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Tuning the Coherent Propagation of Organic Exciton‐Polaritons through Dark State Delocalization

Advanced Science, Journal Year: 2022, Volume and Issue: 9(18)

Published: April 27, 2022

Abstract While there have been numerous reports of long‐range polariton transport at room‐temperature in organic cavities, the spatiotemporal evolution propagation is scarcely reported, particularly initial coherent sub‐ps regime, where photon and exciton wavefunctions are inextricably mixed. Hence detailed process exciton‐polariton and, particular, role dark states has remained poorly understood. Here, femtosecond transient absorption microscopy used to directly image motion microcavities varying quality factor. The found be well‐described by a model band‐like an initially Gaussian distribution exciton‐polaritons real space. velocity polaritons reaches values ≈ 0.65 × 10 6 m s −1 , substantially lower than expected from dispersion. Further, it that proportional factor microcavity. This unexpected link between quality‐factor suggested result admixing delocalized states.

Language: Английский

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The Rise and Current Status of Polaritonic Photochemistry and Photophysics

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(18), P. 10877 - 10919

Published: Sept. 8, 2023

The interaction between molecular electronic transitions and electromagnetic fields can be enlarged to the point where distinct hybrid light-matter states, polaritons, emerge. photonic contribution these states results in increased complexity as well an opening modify photophysics photochemistry beyond what normally seen organic molecules. It is today evident that polaritons offer opportunities for photophysics, which has caused ever-rising interest field. Focusing on experimental landmarks, this review takes its reader from advent of field polaritonic chemistry, over split into polariton chemistry photochemistry, present day status within photophysics. To introduce field, starts with a general description interactions, how enhance these, characterizes coupling strength. Then strongly coupled systems using Fabry-Perot plasmonic cavities are described. This followed by room-temperature Bose-Einstein condensation/polariton lasing systems. ends discussion benefits, limitations, future developments strong exciton-photon

Language: Английский

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Ultrafast imaging of polariton propagation and interactions

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 30, 2023

Abstract Semiconductor excitations can hybridize with cavity photons to form exciton-polaritons (EPs) remarkable properties, including light-like energy flow combined matter-like interactions. To fully harness these EPs must retain ballistic, coherent transport despite matter-mediated interactions lattice phonons. Here we develop a nonlinear momentum-resolved optical approach that directly images in real space on femtosecond scales range of polaritonic architectures. We focus our analysis EP propagation layered halide perovskite microcavities. reveal EP–phonon lead large renormalization velocities at high excitonic fractions room temperature. Despite strong interactions, ballistic is maintained for up half-exciton EPs, agreement quantum simulations dynamic disorder shielding through light-matter hybridization. Above 50% character, rapid decoherence leads diffusive transport. Our work provides general framework precisely balance coherence, velocity, and

Language: Английский

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Molecular Chemistry in Cavity Strong Coupling

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(13), P. 8099 - 8126

Published: June 30, 2023

The coherent exchange of energy between materials and optical fields leads to strong light-matter interactions so-called polaritonic states with intriguing properties, halfway light matter. Two decades ago, research on these interactions, using cavity (vacuum) fields, remained for the most part province physicist, a focus inorganic requiring cryogenic temperatures carefully fabricated, high-quality cavities their study. This review explores history recent acceleration interest in application molecular properties processes. enormous collective oscillator strength dense films organic molecules, aggregates, allows vacuum field coupling be achieved at room temperature, even rapidly highly lossy metallic cavities. has put associated phenomena fingertips laboratory chemists, scientists, biochemists as potentially new tool control chemistry. exciting that have emerged suggest are genuine relevance within material landscape.

Language: Английский

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Molecular Polaritons for Chemistry, Photonics and Quantum Technologies

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(5), P. 2512 - 2552

Published: Feb. 28, 2024

Molecular polaritons are quasiparticles resulting from the hybridization between molecular and photonic modes. These composite entities, bearing characteristics inherited both constituents, exhibit modified energy levels wave functions, thereby capturing attention of chemists in past decade. The potential to modify chemical reactions has spurred many investigations, alongside efforts enhance manipulate optical responses for quantum applications. This Review centers on experimental advances this burgeoning field. Commencing with an introduction fundamentals, including theoretical foundations various cavity architectures, we discuss outcomes polariton-modified reactions. Furthermore, navigate through ongoing debates uncertainties surrounding underpinning mechanism innovative method controlling chemistry. Emphasis is placed gaining a comprehensive understanding dynamics polaritons, particular, vibrational polaritons─a pivotal facet steering Additionally, unique capability coherent two-dimensional spectroscopy dissect polariton dark mode dynamics, offering insights into critical components within that alter We further expand utility applications as well precise manipulation polarizations, notably context chiral phenomena. discussion aspires ignite deeper curiosity engagement revealing physics properties, broad fascination harnessing environments control

Language: Английский

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Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(3), P. 1214 - 1227

Published: Jan. 30, 2024

Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment polaritons requires the matter photon freedom on equal quantum mechanical footing. In limit electronic ultrastrong coupling one few molecules, it is desirable treat using tools ab initio chemistry, yielding an approach we refer cavity electrodynamics, where are treated at level electrodynamics. Here, present called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory provide ground- excited-state polaritonic surfaces with balanced description correlation effects photonic This method provides platform for electrodynamics when both electron light–matter important step toward computational approaches that yield multiple energy couplings can be leveraged dynamics simulations polariton chemistry.

Language: Английский

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

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(1)

Published: Jan. 7, 2025

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 HTC Hamiltonian, which allows reduce cost acting Hamiltonian onto state vector linear order number states, instead quadratic order. second is applying well-known Chebyshev series expansion approach for propagation in system; this us use much larger time step only requires few recursive operations on vectors. These approaches are can be applied any trajectory-based non-adiabatic methods. apply these with our previously developed Lindblad-partially linearized density matrix absorption system, both inhomogeneous site energy disorders dipolar orientational disorders. Our numerical results agree well previous analytic work.

Language: Английский

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Quantum Dynamics Simulations of Exciton Polariton Transport

Nano Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

Recent experiments have shown that exciton transport can be significantly enhanced through hybridization with confined photonic modes in a cavity. The light-matter generates exciton-polariton (EP) bands, whose group velocity is larger than the excitons. Dissipative mechanisms affect constituent states of EPs, such as exciton–phonon coupling and cavity loss, been observed to reduce velocities experiments. To elucidate impacts these dissipative on polariton transport, we developed an efficient quantum dynamics approach allows us directly simulate under collective regime beyond long-wavelength approximation. Our numerical results suggest renormalization stronger strengths smaller Q-factor. We observe transition from ballistic diffusive propagation well quality-factor-dependent behavior transient mean square displacement, agreeing recent experimental measurements.

Language: Английский

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