Impact of Dipole Self-Energy on Cavity-Induced Nonadiabatic Dynamics

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

The coupling of matter to the quantized electromagnetic field a plasmonic or optical cavity can be harnessed modify and control chemical physical properties molecules. In cavities, term known as dipole self-energy (DSE) appears in Hamiltonian ensure gauge invariance. aim this work is twofold. First, we introduce method, which has its own merits complements existing methods, compute DSE. Second, study impact DSE on cavity-induced nonadiabatic dynamics realistic system. For that purpose, various matrix elements are computed functions nuclear coordinates system after laser excitation investigated. induce conical intersections between polaritons, gives rise substantial effects. shown slightly affect these light-induced and, particular, break their symmetry.

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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Machine Learning for Polaritonic Chemistry: Accessing Chemical Kinetics

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5402 - 5413

Опубликована: Фев. 14, 2024

Altering chemical reactivity and material structure in confined optical environments is on the rise, yet, a conclusive understanding of microscopic mechanisms remains elusive. This originates mostly from fact that accurately predicting vibrational reactive dynamics for soluted ensembles realistic molecules no small endeavor, adding (collective) strong light–matter interaction does not simplify matters. Here, we establish framework based combination machine learning (ML) models, trained using density-functional theory calculations molecular to accelerate such simulations. We then apply this approach evaluate coupling, changes reaction rate constant, their influence enthalpy entropy deprotection 1-phenyl-2-trimethylsilylacetylene, which has been studied previously both experimentally ab initio While find qualitative agreement with critical experimental observations, especially regard kinetics, also differences comparison previous theoretical predictions. The features ML-accelerated simulations agree show estimated kinetic behavior. Conflicting indicate contribution dynamic electronic polarization process more relevant than currently believed. Our work demonstrates practical use ML polaritonic chemistry, discusses limitations common approximations, paves way holistic description chemistry.

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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Collective Strong Coupling Modifies Aggregation and Solvation

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(5), С. 1428 - 1434

Опубликована: Янв. 30, 2024

Intermolecular (Coulombic) interactions are pivotal for aggregation, solvation, and crystallization. We demonstrate that the collective strong coupling of several molecules to a single optical mode results in notable changes molecular excitations around perturbed molecule, thus representing an impurity otherwise ordered system. A competition between short-range coulombic long-range photonic correlations inverts local transition density polaritonic state, suggesting polarizability solvation shell. Our provide alternative perspective on recent work chemistry pave way rigorous treatment cooperative effects

Язык: Английский

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Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(3)

Опубликована: Янв. 16, 2025

Accurate rovibrational molecular models are employed to gain insight in high-resolution into the collective effects and intermolecular processes arising when molecules gas phase interact with a resonant infrared (IR) radiation mode. An efficient theoretical approach is detailed, numerical results presented for HCl, H2O, CH4 confined an IR cavity. It shown that by employing rotationally resolved model molecules, revealing various cavity-mediated interactions between field-free eigenstates, it possible obtain detailed understanding of physical governing energy level structure, absorption spectra, dynamic behavior systems. Collective effects, due interaction identified shifts, intensity borrowing transfer occurring during Hermitian or non-Hermitian time propagation.

Язык: Английский

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Ab Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems

Journal of Chemical Theory and Computation, Год журнала: 2023, Номер 19(24), С. 9278 - 9289

Опубликована: Дек. 12, 2023

Recent experiments have revealed the profound effect of strong light-matter interactions in optical cavities on electronic ground state molecular systems. This phenomenon, known as vibrational coupling, can modify reaction rates and induce formation polaritons, hybrid states involving both photon modes, modes molecules. We present an ab initio methodology based cavity Born-Oppenheimer Hartree-Fock ansatz, which is specifically powerful for ensembles molecules, to calculate vibro-polaritonic IR spectra. method allows a comprehensive analysis these states. Our semiclassical approach, validated against full quantum simulations, reproduces key features The underlying analytic gradients also allow optimization cavity-coupled systems performing dynamics simulations.

Язык: Английский

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A Quantum Chemistry Approach to Linear Vibro-Polaritonic Infrared Spectra with Perturbative Electron–Photon Correlation

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(8), С. 2262 - 2269

Опубликована: Фев. 21, 2024

In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, polaritons, with characteristic infrared (IR) spectroscopic signatures. Here, we introduce a quantum chemistry-based computational scheme for linear IR spectra of polaritons in polyatomic molecules, which perturbatively accounts nonresonant electron-photon interactions under VSC. Specifically, formulate Born-Oppenheimer perturbation theory (CBO-PT) response approach, provides an approximate but systematic description such correlation effects VSC scenarios while relying on ab initio chemistry methods. We identify relevant at second order CBO-PT, manifest as static polarizability-dependent Hessian corrections emerging intensity component providing access to transmission commonly measured vibro-polaritonic chemistry. Illustratively, address CO2 Fe(CO)5 models sound agreement nonperturbative CBO theory.

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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