Cavity quantum materials

Applied Physics Reviews, Journal Year: 2022, Volume and Issue: 9(1)

Published: Feb. 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.

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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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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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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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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Simulating molecular polaritons in the collective regime using few-molecule models

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(15)

Published: April 6, 2023

The study of molecular polaritons beyond simple quantum emitter ensemble models (e.g., Tavis-Cummings) is challenging due to the large dimensionality these systems and complex interplay electronic nuclear degrees freedom. This complexity constrains existing either coarse-grain rich physics chemistry freedom or artificially limit description a small number molecules. In this work, we exploit permutational symmetries drastically reduce computational cost ab initio dynamics simulations for N. Furthermore, discover an emergent hierarchy timescales present in systems, that justifies use effective single molecule approximately capture entire ensemble, approximation becomes exact as N → ∞. We also systematically derive finite corrections show addition k extra molecules enough account phenomena whose rates scale 풪(N-k). Based on result, discuss how seamlessly modify single-molecule strong coupling describe corresponding ensemble. call approach collective using truncated equations (CUT-E), benchmark it against well-known results polariton relaxation rates, apply universal cavity-assisted energy funneling mechanism between different species. Beyond being computationally efficient tool, formalism provides intuitive picture understanding role bright dark states chemical reactivity, necessary generate robust strategies chemistry.

Language: Английский

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Unraveling a Cavity-Induced Molecular Polarization Mechanism from Collective Vibrational Strong Coupling

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(19), P. 5208 - 5214

Published: May 8, 2024

We demonstrate that collective vibrational strong coupling of molecules in thermal equilibrium can give rise to significant local electronic polarizations the thermodynamic limit. do so by first showing full nonrelativistic Pauli–Fierz problem an ensemble strongly coupled dilute-gas limit reduces cavity Born–Oppenheimer approximation a cavity–Hartree equation for structure. Consequently, each individual molecule experiences self-consistent dipoles all other molecules, which amount non-negligible values (large ensembles). Thus, alter localized "hotspots" within ensemble. Moreover, discovered cavity-induced polarization pattern possesses zero net polarization, resembles continuous form spin glass (or better glass). Our findings suggest thorough understanding polaritonic chemistry, requires treatment dressed structure, numerous, far overlooked, physical mechanisms.

Language: Английский

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Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 8, 2024

Abstract Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules materials. However, probing how electronics dynamics molecular systems change under strong coupling has been challenging due narrow range spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational (VSC) are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC shown influence equilibrium between two conformations balance sensitive London dispersion forces, revealing an apparent constant VSC. In all compounds studied, does not induce detectable changes chemical shifts, J‐couplings, or spin‐lattice relaxation times. This unexpected finding indicates substantially affect electron density distributions, turn profound implications possible mechanisms at play polaritonic suggests emergence collective behavior critical.

Language: Английский

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Analytic model reveals local molecular polarizability changes induced by collective strong coupling in optical cavities

Physical Review Research, Journal Year: 2025, Volume and Issue: 7(1)

Published: March 5, 2025

Despite recent numerical evidence, one of the fundamental theoretical mysteries polaritonic chemistry is how and if collective strong coupling can induce local changes electronic structure to modify chemical properties. Here we present nonperturbative analytic results for a model system consisting an ensemble N harmonic molecules under vibrational (VSC) that alters our understanding this question. By applying cavity Born-Oppenheimer partitioning on Pauli-Fierz Hamiltonian in dipole approximation, dressed many-molecule problem be solved nonperturbatively analytically dilute limit, i.e., self-consistent solution with mean-field Hartree-product wave function becomes exact. We discover molecular polarizabilities are modified even case vanishingly small single-molecule couplings. Consequently, polarization mechanism persists large-N limit. In contrast, perturbative calculation based uncoupled leads qualitatively erroneous scaling behavior vanishing effects large-N Nevertheless, exact (self-consistent) determined from simulations instead. Our observations demonstrate hitherto existing collective-scaling arguments insufficient they pave way refined single- (or few-)molecule strong-coupling systems coupling. Published by American Physical Society 2025

Language: Английский

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Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(3)

Published: Jan. 16, 2025

Accurate rovibrational molecular models are employed to gain insight in high-resolution into the collective effects and intermolecular processes arising when molecules gas phase interact with a resonant infrared (IR) radiation mode. An efficient theoretical approach is detailed, numerical results presented for HCl, H2O, CH4 confined an IR cavity. It shown that by employing rotationally resolved model molecules, revealing various cavity-mediated interactions between field-free eigenstates, it possible obtain detailed understanding of physical governing energy level structure, absorption spectra, dynamic behavior systems. Collective effects, due interaction identified shifts, intensity borrowing transfer occurring during Hermitian or non-Hermitian time propagation.

Language: Английский

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