Polariton chemistry: controlling molecular dynamics with optical cavities

Chemical Science, Год журнала: 2018, Номер 9(30), С. 6325 - 6339

Опубликована: Янв. 1, 2018

Strong coupling of molecules with confined electromagnetic fields provides novel strategies to control chemical reactivity and spectroscopy.

Язык: Английский

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Manipulating matter by strong coupling to vacuum fields

Science, Год журнала: 2021, Номер 373(6551)

Опубликована: Июль 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

Язык: Английский

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Strong light–matter interactions: a new direction within chemistry

Chemical Society Reviews, Год журнала: 2019, Номер 48(3), С. 937 - 961

Опубликована: Янв. 1, 2019

It is possible to modify the chemical and physical properties of molecules, not only through modifications but also by coupling molecules strongly light. More intriguingly, strong between light even without presence a photon. The phenomenon that makes this called vacuum fluctuations, which finite zero point energy quantized electromagnetic field inside an optical cavity. light-matter coupling, can be as large 1 eV (100 kJ mol-1), leads formation new hybrid states, polaritons. formed states viewed linear combination (vacuum field) matter (molecules), thus completely changing landscape system. Using interactions have for instance been used change reactivity, charge conductivity, excited state relaxation pathways rates reactions organic molecules. In review brief history given, followed theoretical framework, methods analysis, accomplishments. Finally, personal reflection on future perspectives applications within given.

Язык: Английский

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Strong light-matter coupling in quantum chemistry and quantum photonics

Nanophotonics, Год журнала: 2018, Номер 7(9), С. 1479 - 1501

Опубликована: Сен. 1, 2018

Abstract In this article, we review strong light-matter coupling at the interface of materials science, quantum chemistry, and photonics. The control light heat thermodynamic limits enables exciting new opportunities for rapidly converging fields polaritonic chemistry optics atomic scale from a theoretical computational perspective. Our follows remarkable experimental demonstrations that now routinely achieve limit matter. many molecules couple collectively to single-photon mode, whereas, in field nanoplasmonics, can be achieved single-molecule limit. Theoretical approaches address these experiments, however, are more recent come spectrum merging developments electrodynamics alike. We latest highlight common features between two different limits, maintaining focus on tools used analyze classes systems. Finally, present perspective need steps toward merging, formally computationally, most prominent Nobel Prize-winning theories physics chemistry: electronic structure (density functional) theory. case how fully description matter treats electrons, photons, phonons same quantized footing will unravel effects cavity-controlled chemical dynamics, optomechanics, nanophotonics, other use phonons.

Язык: Английский

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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 frequency-dependent theory for vibrational polariton chemistry

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Фев. 26, 2021

Recent experiments demonstrate the control of chemical reactivities by coupling molecules inside an optical microcavity. In contrast, transition state theory predicts no change reaction barrier height during this process. Here, we present a theoretical explanation cavity modification ground reactivity in vibrational strong (VSC) regime polariton chemistry. Our results suggest that VSC kinetics is originated from non-Markovian dynamics radiation mode couples to molecule, leading dynamical caging effect coordinate and suppression rate constant for specific range photon frequency close frequency. We use simple analytical describe single molecular system coupled mode. accuracy performing direct numerical calculations transmission coefficients with same model molecule-cavity hybrid system. simulations provide plausible dependent

Язык: Английский

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

ACS Photonics, Год журнала: 2020, Номер 7(4), С. 975 - 990

Опубликована: Фев. 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.

Язык: Английский

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From Optical to Chemical Hot Spots in Plasmonics

Accounts of Chemical Research, Год журнала: 2019, Номер 52(9), С. 2525 - 2535

Опубликована: Авг. 20, 2019

ConspectusIn recent years, the possibility to induce chemical transformations by using tunable plasmonic modes has opened question of whether we can control or create hot spots in these systems. This be rationalized as reactive analogue well-established concept optical spots, which have drawn a great deal attention nanostructures for their ability circumvent far-field diffraction limit conventional elements.Although mainly defined geometry and permittivity nanostructures, degrees freedom influencing photocatalytic properties appear much more numerous. In fact, reactivity systems are deeply influenced dynamics interplay photons, plasmon-polaritons, carriers, phonons, molecular states. These affect reaction rates, product selectivity, spatial localization reaction. this Account, discuss oportunities tuning cascade events that follows excitation decay nanostructures.We series techniques spatially map image nanoscale at single photocatalyst level. We show how optimize carriers manipulating mechanisms nanoparticles. addition, tailored generation non-thermal phonons metallic dissipation is shown promise understand exploit thermal photocatalysis nanoscale. Understanding controlling processes essential rational design solar nanometric photocatalysts.Nevertheless, ultimate capability trigger correlated its navigate through, even modify, potential energy surface given Here reunite both worlds, photocatalysts ones, identifying different transfer pathways influence on selectivity efficiency reactions. foresee migration from will greatly assist understanding ongoing chemistry.

Язык: Английский

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Tracking Polariton Relaxation with Multiscale Molecular Dynamics Simulations

The Journal of Physical Chemistry Letters, Год журнала: 2019, Номер 10(18), С. 5476 - 5483

Опубликована: Авг. 27, 2019

When photoactive molecules interact strongly with confined light modes in optical cavities, new hybrid light–matter states form. They are known as polaritons and correspond to coherent superpositions of excitations the cavity photon. The polariton energies thus potential energy surfaces changed respect bare molecules, such that formation is considered a promising paradigm for controlling photochemical reactions. To effectively manipulate photochemistry light, need remain polaritonic state long enough reaction on modified surface take place. understand what determines this lifetime, we have performed atomistic molecular dynamics simulations room-temperature ensembles rhodamine chromophores coupled single mode 15 fs lifetime. We investigated three popular experimental scenarios followed relaxation after optically pumping (i) lower polariton, (ii) upper or (iii) uncoupled states. results suggest lifetimes accessible limited by ultrafast photoemission due low lifetime reversible population transfer into "dark" manifold. Dark but much smaller contributions from photon, decreasing their emission rates hence increasing lifetimes. find between dark determined overlap absorption spectra. Importantly, excitation can also be transferred "upward" dark-state reservoir broad spectra chromophores, contrary common conception these processes "one-way" down polariton. Our chemistry relying taking place within manifold requires cavities sufficiently and, at same time, strong coupling strengths prevent back-transfer

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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