Inverting singlet and triplet excited states using strong light-matter coupling

Science Advances, Journal Year: 2019, Volume and Issue: 5(12)

Published: Dec. 6, 2019

Molecules sandwiched in an optical cavity can form hybrid light-matter states at energies below the dark spin triplet state.

Language: Английский

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Investigating New Reactivities Enabled by Polariton Photochemistry

The Journal of Physical Chemistry Letters, Journal Year: 2019, Volume and Issue: 10(18), P. 5519 - 5529

Published: Sept. 1, 2019

We perform quantum dynamics simulations to investigate new chemical reactivities enabled by cavity electrodynamics. The light-matter interactions between the molecule and quantized radiation mode inside an optical create a set of hybridized electronic-photonic states, so-called polaritons. polaritonic states adapt curvatures from both ground excited electronic opening up possibilities control photochemical reactions exploiting intrinsic behaviors interactions. With simulations, we demonstrate that selectivity model photoisomerization reaction can be controlled tuning photon frequency or coupling strength, providing ways manipulate via interaction. further collective effects multiple molecules. Our results suggest in resonance case, is recycled among molecules enable state reactions, thus effectively functioning as catalyst. In nonresonance emit absorb virtual photons initiate through fundamental electrodynamics processes. These reveal basic principles polariton photochemistry well promising take advantage photons.

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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Bose–Einstein Condensation of Exciton-Polaritons in Organic Microcavities

Annual Review of Physical Chemistry, Journal Year: 2020, Volume and Issue: 71(1), P. 435 - 459

Published: March 3, 2020

Bose-Einstein condensation describes the macroscopic occupation of a single-particle mode: condensate. This state can in principle be realized for any particles obeying statistics; this includes hybrid light-matter excitations known as polaritons. Some unique optoelectronic properties organic molecules make them especially well suited realization polariton condensates. Exciton-polaritons form optical cavities when electronic couple collectively to mode supported by cavity. These polaritons obey bosonic statistics at moderate densities, are stable room temperature, and have been observed condensed or lasing state. Understanding optimal conditions requires careful modeling complex photophysics molecules. In article, we introduce basic physics exciton-polaritons review experiments demonstrating molecular materials.

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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Quantum Nanophotonics in Two-Dimensional Materials

ACS Photonics, Journal Year: 2021, Volume and Issue: 8(1), P. 85 - 101

Published: Jan. 7, 2021

The field of two-dimensional (2D) materials-based nanophotonics has been growing at a rapid pace, triggered by the ability to design nanophotonic systems with in situ control, unprecedented number degrees freedom, and build material heterostructures from bottom up atomic precision. A wide palette polaritonic classes have identified, comprising ultraconfined optical fields, even approaching characteristic length-scales single atom. These advances real boost for emerging quantum nanophotonics, where mechanical nature electrons polaritons their interactions become relevant. Examples include nonlocal effects, ultrastrong light–matter interactions, Cherenkov radiation, access forbidden transitions, hydrodynamic single-plasmon nonlinearities, quantization, topological so on. In addition these intrinsic phenomena, 2D can also be used as sensitive probes properties that carries modes or materials its vicinity. Here, act probe otherwise invisible excitations, example, superconductors, new tool monitor existence Berry curvature superlattice effects twisted materials. this Perspective, we present an overview emergent 2D-material provide future perspective on prospects both fundamental phenomena technologies, such sensing, single-photon sources, emitters manipulation. We address four main implications: (i) featuring superconductivity explore electronic transport behaviors, (ii) technologies harnessing generation, manipulation, detection using materials, (iii) polariton engineering enabled twist angle stacking order control van der Waals heterostructures, (iv) extreme light−matter strong confinement light level which tools manipulate fields nanoscale (e.g., chemistry, high Purcell enhancement).

Language: Английский

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Reproducibility of cavity-enhanced chemical reaction rates in the vibrational strong coupling regime

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(19)

Published: May 18, 2021

One of the most exciting and debated aspects polariton chemistry is possibility that chemical reactions can be catalyzed by vibrational strong coupling (VSC) with confined optical modes in absence external illumination. Here, we report an attempt to reproduce enhanced rate cyanate ion hydrolysis reported Hiura et al. [chemRxiv:7234721 (2019)] when collective OH stretching vibrations water (which both solvent a reactant) are strongly coupled Fabry–Pérot cavity mode. Using piezo-tunable microcavity, vacuum Rabi splitting but fail observe any change reaction as thickness tuned out regime during given experiment. These findings suggest there subtleties involved successfully realizing VSC-catalyzed kinetics therefore motivate broader effort within community validate claims dark.

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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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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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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