Molecular Polaritonics: Chemical Dynamics Under Strong Light–Matter Coupling

Annual Review of Physical Chemistry, Год журнала: 2021, Номер 73(1), С. 43 - 71

Опубликована: Дек. 6, 2021

Chemical manifestations of strong light-matter coupling have recently been a subject intense experimental and theoretical studies. Here we review the present status this field. Section 1 is an introduction to molecular polaritonics collective response aspects interactions. 2 provides overview key observations these effects, while 3 describes our current understanding effect on chemical dynamics. A brief outline applications energy conversion processes given in 4. Pending technical issues construction approaches are briefly described 5. Finally, summary 6 outlines paths ahead exciting endeavor.

Язык: Английский

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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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Theoretical Challenges in Polaritonic Chemistry

ACS Photonics, Год журнала: 2022, Номер 9(4), С. 1096 - 1107

Опубликована: Фев. 15, 2022

Polaritonic chemistry exploits strong light-matter coupling between molecules and confined electromagnetic field modes to enable new chemical reactivities. In systems displaying this functionality, the choice of cavity determines both confinement number that are involved in process. While wavelength-scale optical cavities interaction is ruled by collective effects, plasmonic subwavelength nanocavities allow even single reach coupling. Due these very distinct situations, a multiscale theoretical toolbox then required explore rich phenomenology polaritonic chemistry. Within framework, each component system (molecules modes) needs be treated sufficient detail obtain reliable results. Starting from general aspects light-molecule interactions typical experimental setups, we underline basic concepts should taken into account when operating area research. Building on considerations, provide map tools already available tackle applications molecular polaritons at different scales. Throughout discussion, draw attention successes challenges still ahead description

Язык: Английский

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Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11191 - 11229

Опубликована: Сен. 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

Язык: Английский

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Spatial Decoupling of Redox Chemistry for Efficient and Highly Selective Amine Photoconversion to Imines

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7181 - 7189

Опубликована: Март 24, 2023

Light-driven primary amine oxidation to imines integrated with H2 production presents a promising means simultaneous of high-value-added fine chemicals and clean fuels. Yet, the effectiveness this strategy is generally limited by poor charge separation photocatalysts uncontrolled hydrogenation secondary amines. Herein, spatial decoupling proposed isolate redox chemistry at distinct sites photocatalysts, CoP core–ZnIn2S4 shell (CoP@ZnIn2S4) coaxial nanorods are assembled as proof-of-concept photocatalyst. Directional ultrafast carrier occurs between core ZnIn2S4 shell, confirmed in situ X-ray photoelectron spectroscopy, surface photovoltage transient absorption spectroscopy analyses. Toward photoconversion model substrate benzylamine N-benzylbenzaldimine, CoP@ZnIn2S4 exhibits 48-time higher rate >99% selectivity when compared (ca. 20% selectivity), detailed reaction mechanism has been verified diffuse reflectance infrared Fourier transform spectroscopy.

Язык: Английский

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Quantum dynamical effects of vibrational strong coupling in chemical reactivity

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Май 12, 2023

Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach investigate model of cavity-modified reactions in the condensed phase. The contains coupling reaction coordinate generic solvent, cavity either or non-reactive mode, and lossy modes. Thus, many most important features needed for realistic modeling modification included. We find molecule is optical it essential treat problem mechanically obtain quantitative account alterations reactivity. sizable sharp changes rate constant associated with mechanical splittings resonances. emerge from our simulations closer those observed than previous calculations, even realistically small values loss. work highlights importance fully treatment vibrational polariton chemistry.

Язык: Английский

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

Energy & Environmental Science, Год журнала: 2022, Номер 15(12), С. 4982 - 5016

Опубликована: Янв. 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.

Язык: Английский

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Control, Modulation, and Analytical Descriptions of Vibrational Strong Coupling

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 5020 - 5048

Опубликована: Апрель 5, 2023

Here, we review the design of optical cavities, transient and modulated responses, theoretical models relevant to vibrational strong coupling (VSC). While planar Fabry-Perot cavities remain most common choice for experiments involving polaritons, other choices including plasmonic phononic nanostructures, extended lattice resonances, wavelength-scale three-dimensionally confined dielectric have unique advantages, which are discussed. Next, nonlinear response laser excitation VSC systems revealed by pump-probe 2DIR techniques. The assignment various features observed in these has been an important topic with significant recent progress controversy. modulation means such as ultrafast pulses electrochemical methods is also described. Finally, approaches understanding physics chemistry reviewed eye toward their applicability usefulness. These fall into two main categories: (1) solving eigenmodes system (2) evolutionary techniques transfer-matrix method its generalizations. need quantum describing critically evaluated light current experimental work, discuss circumstances necessitate consideration full in-plane dispersion cavities.

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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