Mapping the dynamics of energy relaxation in exciton–polaritons using ultrafast two-dimensional electronic spectroscopy DOI Open Access
Shaina Dhamija, Minjung Son

Chemical Physics Reviews, Journal Year: 2024, Volume and Issue: 5(4)

Published: Dec. 1, 2024

Exciton–polaritons are quasiparticles that formed by strong interactions between light and electronic transitions of matter. Polariton states exhibit the characteristics both photons matter transitions, which leads to photophysical chemical properties distinct from those observed in pure states, such as enhanced energy transport altered reactivity conductivity. Critical understanding how these exciting phenomena enabled is underlying mechanisms polaritonic associated relaxation pathways. Ultrafast spectroscopic techniques, transient absorption spectroscopy, have been increasingly utilized interrogate rapid dynamics partly light-like, short-lived albeit with limitations ambiguities. In this review, we discuss two-dimensional an ultrafast technique has underemployed studies exciton–polaritons thus far, can offer detailed insights into primary events not accessible absorption, through analysis off-diagonal cross peaks line shapes.

Language: Английский

Embrace the darkness: An experimental perspective on organic exciton–polaritons DOI Open Access
Thomas Khazanov, Suman Gunasekaran, Aleesha George

et al.

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

Citations

23
Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling DOI
Inki Lee,

Sarah R. Melton,

Ding Xu

et al.

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

Citations

12
Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime DOI Creative Commons
Arpan Dutta, Ville Tiainen, Ilia Sokolovskii

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 4, 2024

Strong coupling between molecules and confined light modes of optical cavities to form polaritons can alter photochemistry, but the origin this effect remains largely unknown. While theoretical models suggest a suppression photochemistry due formation new polaritonic potential energy surfaces, many these do not account for energetic disorder among molecules, which is unavoidable at ambient conditions. Here, we combine simulations experiments show that an ultra-fast photochemical reaction such thermal prevents modification surface radiative decay lossy cavity modes. We also excitation spectrum under strong product bare absorption molecule-cavity system, suggesting act as gateways channeling into molecule, then reacts normally. Our results therefore imply provides means tune action rather than change reaction. The aim chemistry control reactions by placing inside cavities. authors directly possible disorder, in real experiments, mostly channel molecular excitations.

Language: Английский

Citations

11
Unlocking Delocalization: How Much Coupling Strength can Overcome Energy Disorder in Molecular Polaritons? DOI Creative Commons
Tianlin Liu, Guoxin Yin, Wei Xiong

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Polaritons lose delocalization in energetically disordered systems. A large Rabi splitting about 3–4 times of the inhomogeneous linewidths is required to restore delocalization. This study can guide future rational experiment designs.

Language: Английский

Citations

1
Kubo-Anderson theory of polariton line shape DOI
Clàudia Climent, Joseph E. Subotnik, Abraham Nitzan

et al.

Physical review. A/Physical review, A, Journal Year: 2024, Volume and Issue: 109(5)

Published: May 8, 2024

We apply the Kubo-Anderson stochastic theory of molecular spectral line shapes to case polaritons formed in collective strong-coupling regime. investigate both fast and slow limits random frequency modulation emitter as well intermediate regime show how interplay between characteristic timescales cavity disorder is expressed observed shapes. The analytical solution obtained for limit valid any ratio inhomogeneous broadening molecules Rabi splitting, which especially relevant where these two quantities can be same order magnitude.

Language: Английский

Citations

7
More than just smoke and mirrors: Gas-phase polaritons for optical control of chemistry DOI
Jane C. Nelson, Marissa L. Weichman

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(7)

Published: Aug. 15, 2024

Gas-phase molecules are a promising platform to elucidate the mechanisms of action and scope polaritons for optical control chemistry. Polaritons arise from strong coupling dipole-allowed molecular transition with photonic mode an cavity. There is mounting evidence modified reactivity under polaritonic conditions; however, complex condensed-phase environment most experimental demonstrations impedes mechanistic understanding this phenomenon. While gas phase was playground early efforts in atomic cavity quantum electrodynamics, we have only recently demonstrated formation these conditions. Studying isolated gas-phase would eliminate solvent interactions enable state resolution reaction progress. In Perspective, contextualize recent field polariton chemistry offer practical guide design moving forward.

Language: Английский

Citations

4
Continuum model of strong light-matter coupling for molecular polaritons DOI
Suman Gunasekaran, Ryan F. Pinard, Andrew J. Musser

et al.

Physical review. B./Physical review. B, Journal Year: 2025, Volume and Issue: 111(10)

Published: March 31, 2025

Language: Английский

Citations

0
Optical-cavity manipulation strategies of singlet fission systems mediated by conical intersections: Insights from fully quantum simulations DOI

Kewei Sun,

Maxim F. Gelin, Kaijun Shen

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(13)

Published: April 1, 2025

We offer a theoretical perspective on simulation and engineering of polaritonic conical-intersection-driven singlet-fission (SF) materials. begin by examining fundamental models, including Tavis–Cummings Holstein–Tavis–Cummings Hamiltonians, exploring how disorder, non-Hermitian effects, finite temperature conditions impact their dynamics, setting the stage for studying conical intersections crucial role in SF. Using rubrene as an example applying numerically accurate Davydov Ansatz methodology, we derive dynamic spectroscopic responses system demonstrate key mechanisms capable SF manipulation, viz. cavity-induced enhancement/weakening/suppression SF, population localization singlet state via cavity-mode excitation, polaron/polariton decoupling, collective enhancement outline unsolved problems challenges field share our views development future lines research. emphasize significance careful modeling cascades high excitation manifolds envisage that geometric phase effects may remarkably affect dynamics yield. argue microscopic interpretation main regulatory can substantially deepen understanding this process, thereby providing novel ideas solutions improving conversion efficiency photovoltaics.

Language: Английский

Citations

0
Near-UV Tunable Polaritons from Magic-Size Clusters DOI
Aleesha George, River B. Carson, David H. Gracias

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Stronglight-matter coupling to form polaritons has gained significant attention for its applications in materials engineering, optoelectronics, and beyond. The combined properties of their underlying states allow numerous advantages such as delocalization over long distances, room-temperature Bose-Einstein condensation, tunability energy states. Few exciton-polariton systems, however, reach into the UV, identifying ideal that possess large oscillator strengths, exciton binding energies, ease processing, are stable device integration proven challenging. Here, we demonstrate CdS magic-size clusters (MSCs) combine all these traits. Simple solution processing metallic Fabry-Perot (FP) cavities enables MSCs exhibit strong coupling, demonstrated by square root dependence Rabi splitting on chromophore concentration. 390 meV can be achieved, with emission from polariton spanning 3.07 eV (403 nm) 3.64 (340 nm). When splittings normalized excitonic line width, this system is comparable high-performing systems visible range surpasses reported UV systems. absorption establishes a platform develop polaritonic devices across near-UV.

Language: Английский

Citations

0
Unlocking Delocalization: How Much Coupling Strength can Overcome Energy Disorder in Molecular Polaritons? DOI Creative Commons
Tianlin Liu, Guoxin Yin, Wei Xiong

et al.

Published: May 21, 2024

We investigated the criteria to ensure delocalization exists in molecular polaritons – quasiparticles formed from collective strong coupling of light and matter that have shown capabilities modify chemical reactions. Importantly, delocalization, i.e., possess delocalized wavefunctions, is one hallmarks which enables energy transport dynamics. Delocalization polariton systems has been long assumed be robust against disorder ubiquitous real systems. However, this study reveals destroys polaritons. In order mitigate impact disorder, a strength exceeding 3 times inhomogeneous linewidth necessary. When smaller, properties are significantly compromised both static picture dynamic point view. This observation indicates more stringent criterion for preserving unique characteristics compared conventionally adopted standard (collective strengths larger than photonic spectral linewidths). work sheds lights on previous works explain why onset modified dynamics criteria, also serves as an important consideration existing future studies involving high levels disorder.

Language: Английский

Citations

1