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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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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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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Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 8, 2024

Abstract Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules materials. However, probing how electronics dynamics molecular systems change under strong coupling has been challenging due narrow range spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational (VSC) are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC shown influence equilibrium between two conformations balance sensitive London dispersion forces, revealing an apparent constant VSC. In all compounds studied, does not induce detectable changes chemical shifts, J‐couplings, or spin‐lattice relaxation times. This unexpected finding indicates substantially affect electron density distributions, turn profound implications possible mechanisms at play polaritonic suggests emergence collective behavior critical.

Language: Английский

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Machine Learning for Polaritonic Chemistry: Accessing Chemical Kinetics

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5402 - 5413

Published: Feb. 14, 2024

Altering chemical reactivity and material structure in confined optical environments is on the rise, yet, a conclusive understanding of microscopic mechanisms remains elusive. This originates mostly from fact that accurately predicting vibrational reactive dynamics for soluted ensembles realistic molecules no small endeavor, adding (collective) strong light–matter interaction does not simplify matters. Here, we establish framework based combination machine learning (ML) models, trained using density-functional theory calculations molecular to accelerate such simulations. We then apply this approach evaluate coupling, changes reaction rate constant, their influence enthalpy entropy deprotection 1-phenyl-2-trimethylsilylacetylene, which has been studied previously both experimentally ab initio While find qualitative agreement with critical experimental observations, especially regard kinetics, also differences comparison previous theoretical predictions. The features ML-accelerated simulations agree show estimated kinetic behavior. Conflicting indicate contribution dynamic electronic polarization process more relevant than currently believed. Our work demonstrates practical use ML polaritonic chemistry, discusses limitations common approximations, paves way holistic description chemistry.

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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Multi-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling

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

Published: Oct. 19, 2023

Exciton transport can be enhanced in the strong coupling regime where excitons hybridize with confined light modes to form polaritons. Because polaritons have group velocity, their propagation should ballistic and long-ranged. However, experiments indicate that organic propagate a diffusive manner more slowly than velocity. Here, we resolve this controversy by means of molecular dynamics simulations Rhodamine molecules Fabry-Pérot cavity. Our results suggest polariton is limited cavity lifetime appears due reversible population transfers between polaritonic states ballistically at dark are stationary. Furthermore, because long-lived transiently trap excitation, observed on timescales beyond intrinsic lifetime. These insights not only help better understand interpret experimental observations, but also pave way towards rational design molecule-cavity systems for coherent exciton transport.

Language: Английский

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