Manipulating matter by strong coupling to vacuum fields

Science, Journal Year: 2021, Volume and Issue: 373(6551)

Published: July 9, 2021

Captivating cavities Laser technology is a familiar example of how confining light between two mirrors can tune its properties. Quantum mechanics also dictates that even without extraneous light, matter confined in cavity resonant with electronic or vibrational transitions couple vacuum electromagnetic field fluctuations. Garcia-Vidal et al. review the remarkable and still somewhat mysterious implications this “strong-coupling” regime, manifestations ranging from enhanced charge transport to site-selective chemical reactivity across range molecular solid-state materials. Science , abd0336, issue p. eabd0336

Language: Английский

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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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Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 19, 2022

Strong light-matter interaction in cavity environments is emerging as a promising approach to control chemical reactions non-intrusive and efficient manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating reaction has, however, remained unclear, hampering progress this frontier area of research. We leverage quantum-electrodynamical density-functional theory unveil the microscopic behind experimentally observed reduced rate under induced resonant vibrational strong coupling. observe multiple resonances obtain thus far theoretically elusive but critical feature for single strongly coupled molecule undergoing reaction. While we describe only mode do not explicitly account collective coupling intermolecular interactions, qualitative agreement with experimental measurements suggests our conclusions can be largely abstracted towards realization. Specifically, find acts mediator different modes. In effect, energy localized bonds are redistributed differently which ultimately inhibits

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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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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Catalysis by Dark States in Vibropolaritonic Chemistry

Physical Review Letters, Journal Year: 2022, Volume and Issue: 128(9)

Published: Feb. 28, 2022

Collective strong coupling between a disordered ensemble of N localized molecular vibrations and resonant optical cavity mode gives rise to two polariton N-1≫2 dark modes. Thus, experimental changes in thermally activated reaction kinetics due formation appear entropically unlikely remain puzzle. Here we show that the overlooked modes, while parked at same energy as bare vibrations, are robustly delocalized across ∼2-3 molecules, yielding enhanced channels vibrational cooling, concomitantly catalyzing chemical reaction. As an illustration, theoretically ≈50% increase electron transfer rate product stabilization. The reported effects can arise when homogeneous linewidths modes smaller than their spacings.

Language: Английский

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Quantum dynamical effects of vibrational strong coupling in chemical reactivity

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

Published: May 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.

Language: Английский

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