Chemistry under Vibrational Strong Coupling

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(41), С. 16877 - 16889

Опубликована: Окт. 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.

Язык: Английский

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Cavity quantum materials

Applied Physics Reviews, Год журнала: 2022, Номер 9(1)

Опубликована: Фев. 25, 2022

The emergent field of cavity quantum materials bridges collective many-body phenomena in solid state platforms with strong light–matter coupling electrodynamics. This brief review provides an overview the art and highlights recent theoretical proposals first experimental demonstrations control materials. encompasses between electrons modes, superconductivity, phononics ferroelectricity, correlated systems a cavity, light–magnon coupling, topology Hall effect, as well super-radiance. An outlook potential future developments is given.

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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Breakdown of topological protection by cavity vacuum fields in the integer quantum Hall effect

Science, Год журнала: 2022, Номер 375(6584), С. 1030 - 1034

Опубликована: Март 3, 2022

The control of the electronic properties materials via vacuum fields cavity electromagnetic resonators is one emerging frontiers condensed matter physics. We show here that enhancement field fluctuations in subwavelength split-ring dramatically affects arguably most paradigmatic quantum protectorates, namely Hall electron transport high-mobility 2D gases. observed breakdown topological protection integer effect interpreted terms a long-range cavity-mediated hopping where anti-resonant light-matter coupling finally result into finite resistivity induced by fluctuations. present experimental platform can be used for any material and provides new ways to manipulate phases thanks vacuum-field engineering

Язык: Английский

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

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Дек. 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

Язык: Английский

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

Science, Год журнала: 2023, Номер 380(6650), С. 1165 - 1168

Опубликована: Июнь 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.

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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Enabling smart vision with metasurfaces

Nature Photonics, Год журнала: 2022, Номер 17(1), С. 26 - 35

Опубликована: Дек. 22, 2022

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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Vibration-Cavity Polariton Chemistry and Dynamics

Annual Review of Physical Chemistry, Год журнала: 2022, Номер 73(1), С. 429 - 451

Опубликована: Янв. 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.

Язык: Английский

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