Energy cascades in donor-acceptor exciton-polaritons observed by ultrafast two-dimensional white-light spectroscopy

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 27, 2022

Exciton-polaritons are hybrid states formed when molecular excitons strongly coupled to photons trapped in an optical cavity. These systems exhibit many interesting, but not fully understood, phenomena. Here, we utilize ultrafast two-dimensional white-light spectroscopy study donor-acceptor microcavities made from two different layers of semiconducting carbon nanotubes. We observe the delayed growth a cross peak between upper- and lower-polariton bands that is oftentimes obscured by Rabi contraction. simulate spectra use Redfield theory learn energy cascades down manifold new electronic created intermolecular coupling distinct bandgaps donor acceptor. Energy most effectively enters light-matter commensurate with distribution manifold, contributing long-range transfer. Our results broaden understanding transfer dynamics exciton-polariton provide evidence benefits moderately-coupled cavities.

Language: Английский

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Polariton Localization and Dispersion Properties of Disordered Quantum Emitters in Multimode Microcavities

Physical Review Letters, Journal Year: 2023, Volume and Issue: 130(21)

Published: May 24, 2023

Experiments have demonstrated that the strong light-matter coupling in polaritonic microcavities significantly enhances transport. Motivated by these experiments, we solved disordered multimode Tavis-Cummings model thermodynamic limit and used this solution to analyze its dispersion localization properties. The implies wave-vector-resolved spectroscopic quantities can be described single-mode models, but spatially resolved require solution. Nondiagonal elements of Green's function decay exponentially with distance, which defines coherence length. coherent length is strongly correlated photon weight exhibits inverse scaling respect Rabi frequency an unusual dependence on disorder. For energies away from average molecular energy E_{M} above confinement E_{C}, rapidly diverges such it exceeds resonance wavelength λ_{0}. rapid divergence allows us differentiate localized delocalized regimes identify transition diffusive ballistic

Language: Английский

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Multi-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 19, 2023

Exciton transport can be enhanced in the strong coupling regime where excitons hybridize with confined light modes to form polaritons. Because polaritons have group velocity, their propagation should ballistic and long-ranged. However, experiments indicate that organic propagate a diffusive manner more slowly than velocity. Here, we resolve this controversy by means of molecular dynamics simulations Rhodamine molecules Fabry-Pérot cavity. Our results suggest polariton is limited cavity lifetime appears due reversible population transfers between polaritonic states ballistically at dark are stationary. Furthermore, because long-lived transiently trap excitation, observed on timescales beyond intrinsic lifetime. These insights not only help better understand interpret experimental observations, but also pave way towards rational design molecule-cavity systems for coherent exciton transport.

Language: Английский

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Ab initio methods for polariton chemistry

Chemical Physics Reviews, Journal Year: 2023, Volume and Issue: 4(4)

Published: Oct. 11, 2023

Polariton chemistry exploits the strong interaction between quantized excitations in molecules and photon states optical cavities to affect chemical reactivity. Molecular polaritons have been experimentally realized by coupling of electronic, vibrational, rovibrational transitions modes, which has spurred a tremendous theoretical effort model explain how polariton formation can influence chemistry. This tutorial review focuses on computational approaches for electronic problem through combination familiar techniques from ab initio structure theory cavity quantum electrodynamics, toward goal supplying predictive theories Our aim is emphasize relevant details with enough clarity newcomers field follow, present simple practical code examples catalyze further development work.

Language: Английский

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Resonance theory and quantum dynamics simulations of vibrational polariton chemistry

The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 159(8)

Published: Aug. 22, 2023

We present numerically exact quantum dynamics simulations using the hierarchical equation of motion approach to investigate resonance enhancement chemical reactions due vibrational strong coupling (VSC) in polariton chemistry. The results reveal that cavity mode acts like a “rate-promoting mode” enhances ground state reaction rate constant when frequency matches transition frequency. simulation predicts VSC-modified will change quadratically as light–matter strength increases. When changing lifetime from lossy limit lossless limit, predict there be turnover constant. Based on numerical observations, we an analytic theory explain observed sharp peak profile tuning match excited states. This further explains origin broadening profile. agrees with under golden rule and short limit. To best our knowledge, this is first able behavior adiabatic cavity. envision both analysis offer invaluable theoretical insights into fundamental mechanism VSC-induced modifications

Language: Английский

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Embrace the darkness: An experimental perspective on organic exciton–polaritons

Chemical Physics Reviews, Journal Year: 2023, Volume and Issue: 4(4)

Published: Nov. 13, 2023

Organic polaritonics has emerged as a captivating interdisciplinary field that marries the complexities of organic photophysics with fundamental principles quantum optics. By harnessing strong light–matter coupling in materials, exciton–polaritons offer unique opportunities for advanced device performance, including enhanced energy transport and low-threshold lasing, well new functionalities like polariton chemistry. In this review, we delve into foundational from an experimental perspective, highlighting key states, processes, timescales govern phenomena. Our review centers on spectroscopy exciton–polaritons. We overview primary spectroscopic approaches reveal phenomena, discuss challenges disentangling polaritonic signatures spectral artifacts. how due to their complex disordered nature, not only present conventional models but also provide physics, manipulating dark electronic states. As research continues grow, increasingly materials devices, serves valuable introductory guide researchers navigating intricate landscape polaritonics.

Language: Английский

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Collective polaritonic effects on chemical dynamics suppressed by disorder

Physical Review Research, Journal Year: 2024, Volume and Issue: 6(1)

Published: Feb. 29, 2024

We present a powerful formalism, disordered collective dynamics using truncated equations (d-CUT-E), to simulate the ultrafast quantum of molecular polaritons in strong coupling regime, where ensemble N≫106 molecules couples cavity mode. Notably, we can capture this with hosting single molecule ∼Nbins electronic states, Nbins≪N is number bins discretizing disorder distribution. Using d-CUT-E conclude that coupling, as evaluated from linear optical spectra, be poor proxy for polariton chemistry. For highly ensembles, total reaction yield upon broadband excitation identical outside cavity, while narrowband produces distinct yields solely due differences initial states prepared prior reaction. Published by American Physical Society 2024

Language: Английский

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Non-Hermitian molecular dynamics simulations of exciton–polaritons in lossy cavities

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(9)

Published: March 1, 2024

The observation that materials can change their properties when placed inside or near an optical resonator has sparked a fervid interest in understanding the effects of strong light-matter coupling on molecular dynamics, and several approaches have been proposed to extend methods computational chemistry into this regime. Whereas majority these focused modeling single molecule coupled cavity mode, changes so far only observed experimentally very many molecules are collectively multiple modes with short lifetimes. While atomistic simulations performed semi-classical explicit description losses restricted which few degrees freedom were considered. Here, we implemented effective non-Hermitian Hamiltonian explicitly treat large-scale dynamics organic polaritons used it perform both mean-field surface hopping polariton relaxation, propagation, energy transfer.

Language: Английский

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Controlling the Manifold of Polariton States Through Molecular Disorder

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: 12(11)

Published: Jan. 15, 2024

Abstract Exciton polaritons, arising from the interaction of electronic transitions with confined electromagnetic fields, have emerged as a powerful tool to manipulate properties organic materials. However, standard experimental and theoretical approaches overlook significant energetic disorder present in most materials now studied. Using conjugated polymer P3HT model platform, degree is systematically tuned corresponding redistribution photonic character within polariton manifold observed. Based on these subtle spectral features, more generalized approach developed describe strong light‐matter coupling disordered systems that captures key spectroscopic observables provides description rich states intermediate between bright dark. Applied wide range systems, method challenges prevailing notions about ultrastrong whether it can be achieved broad, absorbers.

Language: Английский

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Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9544 - 9553

Published: March 26, 2024

Strong coupling between photonic modes and molecular electronic excitations, creating hybrid light-matter states called polaritons, is an attractive avenue for controlling chemical reactions. Nevertheless, experimental demonstrations of polariton-modified reactions remain sparse. Here, we demonstrate modified photoisomerization kinetics merocyanine diarylethene by the reactant's optical transition with microcavity modes. We leverage broadband Fourier-plane microscopy to noninvasively rapidly monitor within microcavities, enabling systematic investigation different cavity-exciton detunings photoexcitation conditions. three distinct effects cavity coupling: first, a renormalization density states, akin Purcell effect, leads enhanced absorption isomerization rates at certain wavelengths, notably red-shifting onset photoisomerization. This effect present under both strong weak couplings. Second, kinetic competition polariton localization into reactive losses suppression yield. Finally, our key result that in reaction mixtures multiple reactant isomers, exhibiting partially overlapping transitions pathways, resonance can be tuned funnel photoexcitations specific isomers. Thus, upon decoherence, polaritons localize chosen isomer, selectively triggering latter's despite initially being delocalized across all suggests careful tuning promising steer enhance product selectivity mixtures.

Language: Английский

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