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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Vibrational weak and strong coupling modify a chemical reaction via cavity-mediated radiative energy transfer

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

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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Cavity Born–Oppenheimer Hartree–Fock Ansatz: Light–Matter Properties of Strongly Coupled Molecular Ensembles

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(36), С. 8024 - 8033

Опубликована: Авг. 31, 2023

Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, current understanding of interplay between molecules confined light modes is incomplete. Accurate theoretical models take into account intermolecular interactions to describe ensembles are therefore essential understand mechanisms governing polaritonic chemistry. We present an ab initio Hartree-Fock ansatz in framework Born-Oppenheimer approximation study strongly interacting with cavity. This provides a nonperturbative, self-consistent description coupled molecular ensembles, taking cavity-mediated dipole self-energy contributions. To demonstrate capability ansatz, we collective effects diatomic hydrogen fluoride molecules. Our results highlight importance dipole-dipole interactions, which lead energetic changes individual ensemble.

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

Chemical Physics Reviews, Год журнала: 2023, Номер 4(4)

Опубликована: Ноя. 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.

Язык: Английский

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Resonance theory and quantum dynamics simulations of vibrational polariton chemistry

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(8)

Опубликована: Авг. 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

Язык: Английский

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Collective polaritonic effects on chemical dynamics suppressed by disorder

Physical Review Research, Год журнала: 2024, Номер 6(1)

Опубликована: Фев. 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

Язык: Английский

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Understanding the cavity Born–Oppenheimer approximation

The Journal of Chemical Physics, Год журнала: 2024, Номер 160(18)

Опубликована: Май 8, 2024

Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change properties, such as ground-state reactivity. Theoretical studies toward the origin of this exciting observation roughly be divided into two categories, with based on Hamiltonians simply couple a molecule to cavity mode via its dipole moment one hand, other hand ab initio calculations self-consistently include effect electronic ground state within Born-Oppenheimer (CBO) approximation; these approaches are not equivalent. The CBO approach is more rigorous, but unfortunately it requires rewriting electronic-structure code, results may sometimes hard physically interpret. In work, we exploit relation demonstrate real (hydrogen fluoride) for realistic strengths, recover energies spectra high accuracy using only out-of-cavity quantities from standard calculations. doing so, discover what thephysical effects underlying are. Our methodology aid in incorporating possibly important features models, play pivotal role demystifying results, provide practical efficient alternative full

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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