Unlocking Delocalization: How Much Coupling Strength can Overcome Energy Disorder in Molecular Polaritons?

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 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.

Язык: Английский

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Optical Cavity Enhancement of Visible Light-Driven Photochemical Reaction in the Crystalline State

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Photochemical reactions enable the synthesis of energetically unfavorable compounds but often require irradiation with ultraviolet light, which potentially induces side reactions.

Язык: Английский

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Realistic Ab Initio Predictions of Excimer Behavior under Collective Light-Matter Strong Coupling

Physical Review X, Год журнала: 2025, Номер 15(2)

Опубликована: Май 5, 2025

Experiments show that light-matter strong coupling affects chemical properties, though the underlying mechanism remains unclear. A major challenge is to perform reliable and affordable simulation of molecular behavior when many molecules are collectively coupled same optical mode. This paper presents an quantum electrodynamics cluster method for collective regime. The model describes electronic electron-photon correlation within a subsystem, while simplified description polaritonic excitations allows realistic microscopic coupling. developed framework provides computationally tractable route accurately simulate molecule in environment, which unfeasible several treated explicitly. We investigate properties argon dimer under In single-molecule regime (large coupling), potential energies substantially modified, weakening excimer bond. contrast, (small coupling, large number molecules), ground state energy surface first vibrational levels excited do not change significantly. However, produces abrupt transition landscape excimer, causing higher behave similarly vibrations state. expect formation be inhibited by conclude altered via distinct mechanisms regimes. also discuss fundamental aspects chemistry, such as resonance conditions sudden changes critical strength achieved. Published American Physical Society 2025

Язык: Английский

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Simulating anharmonic vibrational polaritons beyond the long wavelength approximation

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(1)

Опубликована: Янв. 2, 2025

In this work, we investigate anharmonic vibrational polaritons formed due to strong light–matter interactions in an optical cavity between radiation modes and vibrations beyond the long-wavelength limit. We introduce a conceptually simple description of interactions, where spatially localized couple vibrations. Within theoretical framework, employ self-consistent phonon theory dynamical mean-field efficiently simulate momentum-resolved vibrational-polariton spectra, including effects anharmonicity. Numerical simulations model systems demonstrate accuracy applicability our approach.

Язык: Английский

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More than just smoke and mirrors: Gas-phase polaritons for optical control of chemistry

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(7)

Опубликована: Авг. 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.

Язык: Английский

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Polaritonic quantum matter

Nanophotonics, Год журнала: 2025, Номер unknown

Опубликована: Май 5, 2025

Abstract Polaritons are quantum mechanical superpositions of photon states with elementary excitations in molecules and solids. The light–matter admixture causes a characteristic frequency-momentum dispersion shared by all polaritons irrespective the microscopic nature material that could entail charge, spin, lattice or orbital effects. retain strong nonlinearities their matter component simultaneously inherit ray-like propagation light. prompt new properties, enable opportunities for spectroscopy/imaging, empower simulations give rise to forms synthetic matter. Here, we review emergent effects rooted polaritonic quasiparticles wide variety physical implementations. We present broad portfolio platforms phenomena what term discuss unifying aspects across different implementations focus on recent developments in: imaging, cavity electrodynamics materials engineering, topology nonlinearities, as well polaritonics.

Язык: Английский

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Strong Coupling Quantum Electrodynamics Hartree–Fock Response Theory

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

The development of reliable ab initio methods for light-matter strong coupling is necessary a deeper understanding molecular polaritons. recently developed quantum electrodynamics Hartree-Fock model (SC-QED-HF) provides cavity-consistent orbitals, overcoming several difficulties related to the simpler QED-HF wave function. In this paper, we further develop method by implementing response theory SC-QED-HF. We compare derived linear equations with time-dependent and discuss validity equivalence relations connecting matter electromagnetic observables. Our results show that electron-photon correlation induces an excitation redshift compared energies, effect dipole self-energy on ground excited state properties different basis sets.

Язык: Английский

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Electronic strong coupling modifies the ground-state intermolecular interactions in self-assembled chlorin molecules

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Июнь 2, 2025

Язык: Английский

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Unraveling abnormal collective effects via the non-monotonic number dependence of electron transfer in confined electromagnetic fields

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(10)

Опубликована: Сен. 9, 2024

Strong light–matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to possibilities modifying chemical reactivity molecular properties. While responses, such as enhanced Rabi splitting, are often observed, overall effect on systems remains ambiguous for a large number molecules. In this paper, we investigate non-adiabatic electron transfer process in donor–acceptor pairs influenced by excitation local dynamics. Using timescale difference between reorganization thermal fluctuations, derive analytical formulas rate constant polariton relaxation rate. These apply any (N) account induced photon coupling. Our findings reveal non-monotonic dependence N, which can be understood interplay relaxation. As result, cavity-induced quantum yield increases linearly with N small (as predicted simple Dicke model) but shows turnover suppression N. We also interrelate bath frequency molecules, suggesting optimal maximizing enhancement. The analysis provides insight understanding light transfer, helping predict condition effective cavity-controlled reactivity.

Язык: Английский

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