Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11191 - 11229

Published: Sept. 20, 2023

In this review, we present the theoretical foundations and first-principles frameworks to describe quantum matter within electrodynamics (QED) in low-energy regime, with a focus on polaritonic chemistry. By starting from fundamental physical mathematical principles, first review great detail ab initio nonrelativistic QED. The resulting Pauli-Fierz field theory serves as cornerstone for development of (in principle exact but practice) approximate computational methods such quantum-electrodynamical density functional theory, QED coupled cluster, or cavity Born–Oppenheimer molecular dynamics. These treat light equal footing and, at same time, have level accuracy reliability established chemistry electronic structure theory. After an overview key ideas behind those methods, highlight their benefits understanding photon-induced changes chemical properties reactions. Based results obtained by identify open questions how so far missing detailed can be established. We finally give outlook future directions

Language: Английский

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Light–Matter Interactions in Hybrid Material Metasurfaces

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(19), P. 15177 - 15203

Published: June 28, 2022

This Review focuses on the integration of plasmonic and dielectric metasurfaces with emissive or stimuli-responsive materials for manipulating light-matter interactions at nanoscale. Metasurfaces, engineered planar structures rationally designed building blocks, can change local phase intensity electromagnetic waves subwavelength unit level offers more degrees freedom to control flow light. A combination nanoscale emitters facilitates access weak strong coupling regimes enhanced photoluminescence, lasing, controlled quantum emission, formation exciton-polaritons. In addition materials, functional that respond external stimuli be combined engineer tunable nanophotonic devices. Emerging metasurface designs including surface-functionalized, chemically tunable, multilayer hybrid open prospects diverse applications, photocatalysis, sensing, displays, information.

Language: Английский

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Metasurface‐Enhanced Infrared Spectroscopy: An Abundance of Materials and Functionalities

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(34)

Published: May 31, 2022

Infrared spectroscopy provides unique information on the composition and dynamics of biochemical systems by resolving characteristic absorption fingerprints their constituent molecules. Based this inherent chemical specificity capability for label-free, noninvasive, real-time detection, infrared approaches have unlocked a plethora breakthrough applications fields ranging from environmental monitoring defense to analysis medical diagnostics. Nanophotonics has played crucial role pushing sensitivity limits traditional far-field using resonant nanostructures focus incident light into nanoscale hot-spots electromagnetic field, greatly enhancing light-matter interaction. Metasurfaces composed regular arrangements such resonators further increase design space tailoring control both spectrally spatially, which established them as an invaluable toolkit surface-enhanced spectroscopy. Starting fundamental concepts metasurface-enhanced spectroscopy, broad palette resonator geometries, materials, realizing highly sensitive metadevices is showcased, with special emerging phononic 2D van der Waals integration waveguides lab-on-a-chip devices. Furthermore, advanced sensor functionalities metasurface-based including multiresonance, tunability, dielectrophoresis, live cell sensing, machine-learning-aided are highlighted.

Language: Английский

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Recent advances in triplet–triplet annihilation upconversion and singlet fission, towards solar energy applications

Energy & Environmental Science, Journal Year: 2022, Volume and Issue: 15(12), P. 4982 - 5016

Published: Jan. 1, 2022

Here we consolidate recent advances in the fields of triplet–triplet annihilation photon upconversion and singlet fission. We further describe their utility increasing efficiency photovoltaic devices.

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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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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Rovibrational Polaritons in Gas-Phase Methane

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(10), P. 5982 - 5987

Published: March 3, 2023

Polaritonic states arise when a bright optical transition of molecular ensemble is resonantly matched to an cavity mode frequency. Here, we lay the groundwork study behavior polaritons in clean, isolated systems by establishing new platform for vibrational strong coupling gas-phase molecules. We access regime intracavity cryogenic buffer gas cell optimized preparation simultaneously cold and dense ensembles report proof-of-principle demonstration methane. strongly cavity-couple individual rovibrational transitions probe range strengths detunings. reproduce our findings with classical transmission simulations presence absorbers. This infrastructure will provide testbed benchmark studies cavity-altered chemistry.

Language: Английский

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Photonic spin-controlled self-hybridized exciton-polaritons in WS2 metasurfaces driven by chiral quasibound states in the continuum

Physical review. B./Physical review. B, Journal Year: 2024, Volume and Issue: 109(12)

Published: March 7, 2024

Bulk transition metal dichalcogenides (TMDs) have found widespread applications on nanophotonics, condensed matter physics, and quantum optics, due to their high refractive index stable excitonic response at room temperature. In this paper, based the finite-element method simulations, we demonstrate that enables fabrication of bulk $\mathrm{W}{\mathrm{S}}_{2}$ into high-quality-factor metasurfaces support chiral quasibound states in continuum (Q-BICs). Interestingly, Q-BIC resonance can turn hybridize with excitons metasurface itself. The self-hybridized exciton-polaritons, induced by strong coupling between a excitons, exhibit typical anticrossing behavior Rabi splitting up 136.5 meV. Such remarkable is also well elucidated coupled oscillator model. Intriguingly, numerically verify exciton-polaritons are photonic spin-controlled, attributed circular dichroism approaching 0.91. Therefore, control exciton-photon interaction simply changing helicity incident light. We believe outstanding itself, without external microcavities, could pave way for large-scale, low-cost integrated polaritonic devices Additionally, will enrich toolbox engineering interactions TMDs other semiconductors. spin-controlled would find utility ultrafast all-optical switches, modulators, light-emitting devices, valleytronic devices.

Language: Английский

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Impact of Dipole Self-Energy on Cavity-Induced Nonadiabatic Dynamics

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The coupling of matter to the quantized electromagnetic field a plasmonic or optical cavity can be harnessed modify and control chemical physical properties molecules. In cavities, term known as dipole self-energy (DSE) appears in Hamiltonian ensure gauge invariance. aim this work is twofold. First, we introduce method, which has its own merits complements existing methods, compute DSE. Second, study impact DSE on cavity-induced nonadiabatic dynamics realistic system. For that purpose, various matrix elements are computed functions nuclear coordinates system after laser excitation investigated. induce conical intersections between polaritons, gives rise substantial effects. shown slightly affect these light-induced and, particular, break their symmetry.

Language: Английский

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Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(3)

Published: Jan. 16, 2025

Accurate rovibrational molecular models are employed to gain insight in high-resolution into the collective effects and intermolecular processes arising when molecules gas phase interact with a resonant infrared (IR) radiation mode. An efficient theoretical approach is detailed, numerical results presented for HCl, H2O, CH4 confined an IR cavity. It shown that by employing rotationally resolved model molecules, revealing various cavity-mediated interactions between field-free eigenstates, it possible obtain detailed understanding of physical governing energy level structure, absorption spectra, dynamic behavior systems. Collective effects, due interaction identified shifts, intensity borrowing transfer occurring during Hermitian or non-Hermitian time propagation.

Language: Английский

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