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

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(19), С. 5208 - 5214

Опубликована: Май 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.

Язык: Английский

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Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 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.

Язык: Английский

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

Physical Review Research, Год журнала: 2025, Номер 7(1)

Опубликована: Март 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

Язык: Английский

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Non‐Polaritonic Effects in Cavity‐Modified Photochemistry

Advanced Materials, Год журнала: 2023, Номер 36(7)

Опубликована: Ноя. 24, 2023

Abstract Strong coupling of molecules to vacuum fields is widely reported lead modified chemical properties such as reaction rates. However, some recent attempts reproduce infrared strong results have not been successful, suggesting that factors other than may sometimes be involved. In the first vacuum‐modified chemistry experiment, changes a molecular photoisomerization process in ultraviolet‐visible spectral range are attributed visible light. Here, this re‐examined, finding significant variations rates consistent with original work. there no evidence these need coupling. Instead, it suggested involved most strongly influenced by absorption ultraviolet radiation cavity. These indicate care must taken rule out non‐polaritonic effects before invoking explain any arising cavity‐based experiments.

Язык: Английский

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How Quantum is the Resonance Behavior in Vibrational Polariton Chemistry?

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(36), С. 8261 - 8267

Опубликована: Сен. 7, 2023

Recent experiments in polariton chemistry have demonstrated that reaction rates can be modified by vibrational strong coupling to an optical cavity mode. Importantly, this modification occurs only when the frequency of mode is tuned closely match a molecular frequency. This sharp resonance behavior has proved difficult capture theoretically. Only recently did Lindoy et al. [

Язык: Английский

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Resonance theory of vibrational polariton chemistry at the normal incidence

Nanophotonics, Год журнала: 2024, Номер 13(14), С. 2601 - 2615

Опубликована: Фев. 23, 2024

We present a theory that explains the resonance effect of vibrational strong coupling (VSC) modified reaction rate constant at normal incidence Fabry-Pérot (FP) cavity. This analytic is based on mechanistic hypothesis cavity modes promote transition from ground state to excited reactant, which rate-limiting step reaction. mechanism for single molecule coupled single-mode has been confirmed by numerically exact simulations in our recent work [J. Chem. Phys. 159, 084104 (2023)]. Using Fermi's golden rule (FGR), we formulate this many molecules inside FP microcavity. The provides possible explanation condition observed VSC and plausible why only incident angle there effect, whereas, an oblique incidence, no apparent even though both cases generate Rabi splitting forming polariton states. On other hand, current cannot explain collective when large number are collectively cavity, future required build complete microscopic all phenomena VSC.

Язык: Английский

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Investigating the collective nature of cavity-modified chemical kinetics under vibrational strong coupling

Nanophotonics, Год журнала: 2024, Номер 13(14), С. 2617 - 2633

Опубликована: Март 18, 2024

Abstract In this paper, we develop quantum dynamical methods capable of treating the dynamics chemically reacting systems in an optical cavity vibrationally strong-coupling (VSC) limit at finite temperatures and presence a dissipative solvent both few many molecule limits. context two simple models, demonstrate how reactivity collective VSC regime does not exhibit altered rate behavior equilibrium but may resonant modification when system is explicitly out equilibrium. Our results suggest experimental protocols that be used to modify point features included models studied, which demand further scrutiny.

Язык: Английский

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Mechanism of Molecular Polariton Decoherence in the Collective Light–Matter Couplings Regime

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(47), С. 11773 - 11783

Опубликована: Ноя. 18, 2024

Molecular polaritons, the hybridization of electronic states in molecules with photonic excitation inside a cavity, play an important role fundamental quantum science and technology. Understanding decoherence mechanism molecular polaritons is among most significant questions. We theoretically demonstrate that hybridizing many excitons cavity protects overall coherence from phonon-induced decoherence. The polariton time can be prolonged up to 100 fs realistic collective Rabi splitting quality factor at room temperature, compared typical which around 15 fs. Our numerically exact simulations analytic theory suggest dominant population transfer upper state dark manifold. Increasing coupling strength will increase energy gap between these two sets thus prolong lifetime. further derived valuable scaling relations directly indicate how depends on number molecules, splittings, light–matter detunings.

Язык: Английский

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Resonance theory of vibrational strong coupling enhanced polariton chemistry and the role of photonic mode lifetime

Communications Materials, Год журнала: 2024, Номер 5(1)

Опубликована: Июнь 28, 2024

Abstract Recent experiments demonstrate polaritons under the vibrational strong coupling (VSC) regime can modify chemical reactivity. Here, we present a complete theory of VSC-modified rate constants when single molecule to an optical cavity, where role photonic mode lifetime is understood. The analytic expression exhibits sharp resonance behavior, maximum constant reached cavity frequency matches vibration frequency. explains why VSC modification closely resembles spectra outside cavity. Further, discussed temperature dependence constants. agrees well with numerically exact hierarchical equations motion (HEOM) simulations for all explored regimes. Finally, condition at normal incidence considering in-plane momentum inside Fabry-Pérot

Язык: Английский

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Theory and quantum dynamics simulations of exciton-polariton motional narrowing

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(6)

Опубликована: Авг. 9, 2024

The motional narrowing effect has been extensively studied for cavity exciton–polariton systems in recent decades both experimentally and theoretically, which is featured by (1) the subaverage behavior (2) asymmetric linewidths upper polariton lower polariton. However, a minimal theoretical model that clear adequate to address all these effects as well linewidth scaling relations remains missing. In this work, based on single mode 1D Holstein–Tavis–Cummings (HTC) model, we of linear absorption spectra via semi-analytic derivations numerically exact quantum dynamics simulations using hierarchical equations motion approach. results reveal under collective light–matter coupling between N molecules, scales 1/N slow limit, while fast due polaron decoupling effect. Furthermore, varying detunings, exhibit significant narrowing, covering characters mentioned above. Our analytic expressions [Eqs. (34) (35)] agree with numerical parameter regimes explored. These indicate physics adequately accounted single-mode HTC model. We envision expression presented work will offer great value providing better understanding

Язык: Английский

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