Relevance of the Quadratic Diamagnetic and Self-Polarization Terms in Cavity Quantum Electrodynamics

ACS Photonics, Journal Year: 2020, Volume and Issue: 7(4), P. 975 - 990

Published: Feb. 26, 2020

Experiments at the interface of quantum optics and chemistry have revealed that strong coupling between light matter can substantially modify chemical physical properties molecules solids. While theoretical description such situations is usually based on nonrelativistic electrodynamics, which contains quadratic light–matter terms, it commonplace to disregard these terms restrict treatment purely bilinear couplings. In this work, we clarify origin substantial impact most common diamagnetic self-polarization highlight why neglecting them lead rather unphysical results. Specifically, demonstrate their relevance by showing leads loss gauge invariance, basis set dependence, disintegration (loss bound states) any system in limit, radiation ground state, an artificial dependence static dipole. Besides providing important guidance for modeling strongly coupled systems, presented results also indicate conditions under those effects might become accessible.

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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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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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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Theoretical Challenges in Polaritonic Chemistry

ACS Photonics, Journal Year: 2022, Volume and Issue: 9(4), P. 1096 - 1107

Published: Feb. 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

Language: Английский

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Intermolecular interactions in optical cavities: An ab initio QED study

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(9)

Published: March 2, 2021

Intermolecular bonds are weak compared to covalent bonds, but they strong enough influence the properties of large molecular systems. In this work, we investigate how light-matter coupling inside an optical cavity can modify these intermolecular forces. We perform a detailed comparison between currently available ab initio electron-photon methodologies. The electromagnetic field modulate ground state weakly bound complexes. Controlling polarization, interactions be stabilized or destabilized, and electron densities, dipole moments, polarizabilities altered. demonstrate that correlation is fundamental describe in coupling. This work proposes cavities as novel tool manipulate control properties, solvent effects, for molecules materials.

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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Tuning the Coherent Propagation of Organic Exciton‐Polaritons through Dark State Delocalization

Advanced Science, Journal Year: 2022, Volume and Issue: 9(18)

Published: April 27, 2022

Abstract While there have been numerous reports of long‐range polariton transport at room‐temperature in organic cavities, the spatiotemporal evolution propagation is scarcely reported, particularly initial coherent sub‐ps regime, where photon and exciton wavefunctions are inextricably mixed. Hence detailed process exciton‐polariton and, particular, role dark states has remained poorly understood. Here, femtosecond transient absorption microscopy used to directly image motion microcavities varying quality factor. The found be well‐described by a model band‐like an initially Gaussian distribution exciton‐polaritons real space. velocity polaritons reaches values ≈ 0.65 × 10 6 m s −1 , substantially lower than expected from dispersion. Further, it that proportional factor microcavity. This unexpected link between quality‐factor suggested result admixing delocalized states.

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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