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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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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A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity

The Journal of Chemical Physics, Journal Year: 2022, Volume and Issue: 156(23)

Published: May 23, 2022

This Perspective provides a brief introduction into the theoretical complexity of polaritonic chemistry, which emerges from hybrid nature strongly coupled light-matter states. To tackle this complexity, importance ab initio methods is highlighted. Based on those, novel ideas and research avenues are developed with respect to quantum collectivity, as well for resonance phenomena immanent in reaction rates under vibrational strong coupling. Indeed, fundamental questions arise about mesoscopic scale quantum-collectively molecules when considering depolarization shift interpretation experimental data. Furthermore, rationalize recent findings based electrodynamical density-functional theory (QEDFT), simple, but computationally efficient, Langevin framework proposed well-established molecular dynamics. It suggests emergence cavity-induced non-equilibrium nuclear dynamics, where thermal (stochastic) could emerge absence external periodic driving. Overall, we believe that latest results indeed suggest paradigmatic ground-state chemical reactions coupling collective toward more local, (semi)-classically dominated perspective. Finally, various extensions refined description cavity-modified chemistry introduced context QEDFT, future directions field sketched.

Language: Английский

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The Rise and Current Status of Polaritonic Photochemistry and Photophysics

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(18), P. 10877 - 10919

Published: Sept. 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

Language: Английский

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Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(3), P. 1214 - 1227

Published: Jan. 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.

Language: Английский

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Diffusion quantum Monte Carlo approach to the polaritonic ground state

Physical review. A/Physical review, A, Journal Year: 2024, Volume and Issue: 109(3)

Published: March 4, 2024

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent active fields that connects communities chemistry quantum optics. Modeling such phenomena ab initio approaches calls new methodologies, leading to reinvention many commonly used electronic structure methods, as Hartree-Fock, density functional, coupled cluster theories. In this work, we explore formally exact diffusion Monte Carlo approach obtain numerical solutions ground state during dissociation ${\mathrm{H}}_{2}$ molecular system. We examine various electron-nuclear-photon properties throughout dissociation, changes minimum cavity Born-Oppenheimer surface, localization wave function, average mode occupation. Finally, directly compare our results obtained with state-of-the-art, yet approximate, approaches.

Language: Английский

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Strong Coupling Møller–Plesset Perturbation Theory

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Perturbative approaches are methods to efficiently tackle many-body problems, offering both intuitive insights and analysis of correlation effects. However, their application systems where light matter strongly coupled is nontrivial. Specifically, the definition suitable orbitals for zeroth-order Hamiltonian represents a significant theoretical challenge. While reviewing previously investigated orbital choices, this work presents an alternative polaritonic basis strong coupling regime. We develop quantum electrodynamical (QED) Møller–Plesset perturbation theory using obtained from QED Hartree–Fock. assess strengths limitations different with emphasis on frequency strength dispersions, intermolecular interactions polarization orientational The results show essential role consistent molecular framework in order achieve accurate description cavity-induced electron−photon

Language: Английский

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