Chemistry under Vibrational Strong Coupling

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(41), P. 16877 - 16889

Published: Oct. 5, 2021

Over the past decade, possibility of manipulating chemistry and material properties using hybrid light-matter states has stimulated considerable interest. Hybrid can be generated by placing molecules in an optical cavity that is resonant with a molecular transition. Importantly, hybridization occurs even dark because coupling process involves zero-point fluctuations mode (a.k.a. vacuum field) In other words, unlike photochemistry, no real photon required to induce this strong phenomenon. Strong general, but vibrational (VSC) particular, offers exciting possibilities for and, more generally, science. Not only it new tool control chemical reactivity, also gives insight into which vibrations are involved reaction. This Perspective underlying fundamentals coupling, including mini-tutorial on practical issues achieve VSC. Recent advancements "vibro-polaritonic chemistry" related topics presented along challenges field.

Language: Английский

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Molecular Polaritonics: Chemical Dynamics Under Strong Light–Matter Coupling

Annual Review of Physical Chemistry, Journal Year: 2021, Volume and Issue: 73(1), P. 43 - 71

Published: Dec. 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.

Language: Английский

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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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Modification of ground-state chemical reactivity via light–matter coherence in infrared cavities

Science, Journal Year: 2023, Volume and Issue: 380(6650), P. 1165 - 1168

Published: June 15, 2023

Reaction-rate modifications for chemical processes due to strong coupling between reactant molecular vibrations and the cavity vacuum have been reported; however, no currently accepted mechanisms explain these observations. In this work, reaction-rate constants were extracted from evolving transmission spectra, revealing resonant suppression of intracavity reaction rate alcoholysis phenyl isocyanate with cyclohexanol. We observed up an 80% by tuning modes be (NCO) stretch, product carbonyl (CO) cooperative reactant-solvent (CH). These results interpreted using open quantum system model that predicted vibrational distribution reactants canonical statistics as a result light-matter coherences, suggesting links explore chemistry science.

Language: Английский

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Vibration-Cavity Polariton Chemistry and Dynamics

Annual Review of Physical Chemistry, Journal Year: 2022, Volume and Issue: 73(1), P. 429 - 451

Published: Jan. 26, 2022

Molecular polaritons result from light-matter coupling between optical resonances and molecular electronic or vibrational transitions. When the is strong enough, new hybridized states with mixed photon-material character are observed spectroscopically, shifted above below uncoupled frequency. These modes have unique properties can be exploited to promote inhibit physical chemical processes. One remarkable that cavities alter reaction rates product branching ratios no excitation whatsoever. In this work we review ability of vibration-cavity modify processes including reactivity, as well steady-state transient spectroscopy. We discuss larger context these works highlight their most important contributions implications. Our goal provide insight for systematically manipulating in photonic applications.

Language: Английский

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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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Control, Modulation, and Analytical Descriptions of Vibrational Strong Coupling

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 5020 - 5048

Published: April 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.

Language: Английский

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

The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 158(23)

Published: June 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.

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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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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