Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 9786 - 9879

Опубликована: Авг. 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.

Язык: Английский

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The Rise and Current Status of Polaritonic Photochemistry and Photophysics

Chemical Reviews, Год журнала: 2023, Номер 123(18), С. 10877 - 10919

Опубликована: Сен. 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

Язык: Английский

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Swinging between shine and shadow: Theoretical advances on thermally activated vibropolaritonic chemistry

The Journal of Chemical Physics, Год журнала: 2023, Номер 158(23)

Опубликована: Июнь 15, 2023

Polariton chemistry has emerged as an appealing branch of synthetic that promises mode selectivity and a cleaner approach to kinetic control. Of particular interest are the numerous experiments in which reactivity been modified by virtue performing reaction inside infrared optical microcavities absence pumping; this effort is known "vibropolaritonic chemistry." The optimal conditions for these observations (1) resonance between cavity reactive modes at normal incidence (k = 0) (2) monotonic increase effect with concentration emitters sample. Importantly, vibropolaritonic only experimentally demonstrated so-called "collective" strong coupling regime, where there macroscopic number molecules (rather than single molecule) coupled each photon microcavity. Strikingly, efforts understand phenomenon from conceptual standpoint have encountered several roadblocks, no single, unifying theory surfaced thus far. This Perspective documents most relevant approaches taken theorists, laying out contributions unresolved challenges work. We expect not serve primer experimentalists theorists alike but also inform future endeavors quest ultimate formalism chemical kinetics.

Язык: Английский

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Simulating molecular polaritons in the collective regime using few-molecule models

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(15)

Опубликована: Апрель 6, 2023

The study of molecular polaritons beyond simple quantum emitter ensemble models (e.g., Tavis-Cummings) is challenging due to the large dimensionality these systems and complex interplay electronic nuclear degrees freedom. This complexity constrains existing either coarse-grain rich physics chemistry freedom or artificially limit description a small number molecules. In this work, we exploit permutational symmetries drastically reduce computational cost ab initio dynamics simulations for N. Furthermore, discover an emergent hierarchy timescales present in systems, that justifies use effective single molecule approximately capture entire ensemble, approximation becomes exact as N → ∞. We also systematically derive finite corrections show addition k extra molecules enough account phenomena whose rates scale 풪(N-k). Based on result, discuss how seamlessly modify single-molecule strong coupling describe corresponding ensemble. call approach collective using truncated equations (CUT-E), benchmark it against well-known results polariton relaxation rates, apply universal cavity-assisted energy funneling mechanism between different species. Beyond being computationally efficient tool, formalism provides intuitive picture understanding role bright dark states chemical reactivity, necessary generate robust strategies chemistry.

Язык: Английский

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Molecular Chemistry in Cavity Strong Coupling

Chemical Reviews, Год журнала: 2023, Номер 123(13), С. 8099 - 8126

Опубликована: Июнь 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.

Язык: Английский

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Advances in ultrafast plasmonics

Applied Physics Reviews, Год журнала: 2023, Номер 10(2)

Опубликована: Июнь 1, 2023

In the past 20 years, we have reached a broad understanding of many light-driven phenomena in nanoscale systems. The temporal dynamics excited states are instead quite challenging to explore, and, at same time, crucial study for origin fundamental physical and chemical processes. this review, examine current state prospects ultrafast driven by plasmons both from applied point view. This research area is referred as plasmonics represents an outstanding playground tailor control fast optical electronic processes nanoscale, such switching, single photon emission, strong coupling interactions photochemical reactions. Here, provide overview field describe methodologies monitor with timescales terms modeling experimental characterization. Various directions showcased, among others recent advances plasmon-driven chemistry multi-functional plasmonics, which charge, spin, lattice degrees freedom exploited active properties materials. As focus shifts development practical devices, all-optical transistors, also emphasize new materials applications highlight relativistic realm. latter promising potential fusion or particle light sources providing attosecond duration.

Язык: Английский

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

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(19), С. 5208 - 5214

Опубликована: Май 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.

Язык: Английский

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Molecular Polaritons for Chemistry, Photonics and Quantum Technologies

Chemical Reviews, Год журнала: 2024, Номер 124(5), С. 2512 - 2552

Опубликована: Фев. 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

Язык: Английский

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Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(3), С. 1214 - 1227

Опубликована: Янв. 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.

Язык: Английский

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Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 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.

Язык: Английский

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