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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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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Unraveling a Cavity-Induced Molecular Polarization Mechanism from Collective Vibrational Strong Coupling

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(19), P. 5208 - 5214

Published: May 8, 2024

We demonstrate that collective vibrational strong coupling of molecules in thermal equilibrium can give rise to significant local electronic polarizations the thermodynamic limit. do so by first showing full nonrelativistic Pauli–Fierz problem an ensemble strongly coupled dilute-gas limit reduces cavity Born–Oppenheimer approximation a cavity–Hartree equation for structure. Consequently, each individual molecule experiences self-consistent dipoles all other molecules, which amount non-negligible values (large ensembles). Thus, alter localized "hotspots" within ensemble. Moreover, discovered cavity-induced polarization pattern possesses zero net polarization, resembles continuous form spin glass (or better glass). Our findings suggest thorough understanding polaritonic chemistry, requires treatment dressed structure, numerous, far overlooked, physical mechanisms.

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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Diffusion quantum Monte Carlo approach to the polaritonic ground state

Physical review. A/Physical review, A, Journal Year: 2024, Volume and Issue: 109(3)

Published: March 4, 2024

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

Language: Английский

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Gradient High‐Q Dielectric Metasurfaces for Broadband Sensing and Control of Vibrational Light‐Matter Coupling

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: March 21, 2024

Surface-enhanced infrared absorption spectroscopy (SEIRA) has emerged as a powerful technique for ultrasensitive chemical-specific analysis. SEIRA can be realized by employing metasurfaces that enhance light-matter interactions in the spectral bands of molecular vibrations. Increasing sample complexity emphasizes need operate simultaneously at different bands, both accessing rich information over broad band, and resolving subtle differences fingerprints through narrow-band resonances. Here, novel concept resonance-gradient is introduced, where required selectivity achieved via local high-quality-factor (high-Q) resonances, while continuous coverage band enabled gradual adjustment unit-cell dimensions along planar structure. The highly tailorable design gradient provides flexibility shaping sampling density to match relevant target analytes keeping compact device footprint. versatility demonstrated several sensing scenarios, including polymer mixture deconvolution, detecting multistep bioassay, identification onset vibrational strong coupling regime. proposed gradient-resonance platform significantly contributes rapidly evolving landscape nonlocal metasurfaces, enabling applications detection analysis fundamental interaction phenomena.

Language: Английский

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Analytic model reveals local molecular polarizability changes induced by collective strong coupling in optical cavities

Physical Review Research, Journal Year: 2025, Volume and Issue: 7(1)

Published: March 5, 2025

Despite recent numerical evidence, one of the fundamental theoretical mysteries polaritonic chemistry is how and if collective strong coupling can induce local changes electronic structure to modify chemical properties. Here we present nonperturbative analytic results for a model system consisting an ensemble N harmonic molecules under vibrational (VSC) that alters our understanding this question. By applying cavity Born-Oppenheimer partitioning on Pauli-Fierz Hamiltonian in dipole approximation, dressed many-molecule problem be solved nonperturbatively analytically dilute limit, i.e., self-consistent solution with mean-field Hartree-product wave function becomes exact. We discover molecular polarizabilities are modified even case vanishingly small single-molecule couplings. Consequently, polarization mechanism persists large-N limit. In contrast, perturbative calculation based uncoupled leads qualitatively erroneous scaling behavior vanishing effects large-N Nevertheless, exact (self-consistent) determined from simulations instead. Our observations demonstrate hitherto existing collective-scaling arguments insufficient they pave way refined single- (or few-)molecule strong-coupling systems coupling. Published by American Physical Society 2025

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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Cavity Born–Oppenheimer Hartree–Fock Ansatz: Light–Matter Properties of Strongly Coupled Molecular Ensembles

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(36), P. 8024 - 8033

Published: Aug. 31, 2023

Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, current understanding of interplay between molecules confined light modes is incomplete. Accurate theoretical models take into account intermolecular interactions to describe ensembles are therefore essential understand mechanisms governing polaritonic chemistry. We present an ab initio Hartree-Fock ansatz in framework Born-Oppenheimer approximation study strongly interacting with cavity. This provides a nonperturbative, self-consistent description coupled molecular ensembles, taking cavity-mediated dipole self-energy contributions. To demonstrate capability ansatz, we collective effects diatomic hydrogen fluoride molecules. Our results highlight importance dipole-dipole interactions, which lead energetic changes individual ensemble.

Language: Английский

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Theory and modeling of light-matter interactions in chemistry: current and future

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(46), P. 31554 - 31577

Published: Jan. 1, 2023

Light-matter interaction not only plays an instrumental role in characterizing materials' properties via various spectroscopic techniques but also provides a general strategy to manipulate material the design of novel nanostructures. This perspective summarizes recent theoretical advances modeling light-matter interactions chemistry, mainly focusing on plasmon and polariton chemistry. The former utilizes highly localized photon, plasmonic hot electrons, local heat drive chemical reactions. In contrast, chemistry modifies potential energy curvatures bare electronic systems, hence their forming hybrid states, so-called polaritons. starts with basic background interactions, molecular quantum electrodynamics theory, challenges Then, are described, future directions toward multiscale simulations interaction-mediated discussed.

Language: Английский

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