Quantum dynamical effects of vibrational strong coupling in chemical reactivity

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 12, 2023

Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach investigate model of cavity-modified reactions in the condensed phase. The contains coupling reaction coordinate generic solvent, cavity either or non-reactive mode, and lossy modes. Thus, many most important features needed for realistic modeling modification included. We find molecule is optical it essential treat problem mechanically obtain quantitative account alterations reactivity. sizable sharp changes rate constant associated with mechanical splittings resonances. emerge from our simulations closer those observed than previous calculations, even realistically small values loss. work highlights importance fully treatment vibrational polariton chemistry.

Language: Английский

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Molecular Polaritons for Chemistry, Photonics and Quantum Technologies

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(5), P. 2512 - 2552

Published: Feb. 28, 2024

Molecular polaritons are quasiparticles resulting from the hybridization between molecular and photonic modes. These composite entities, bearing characteristics inherited both constituents, exhibit modified energy levels wave functions, thereby capturing attention of chemists in past decade. The potential to modify chemical reactions has spurred many investigations, alongside efforts enhance manipulate optical responses for quantum applications. This Review centers on experimental advances this burgeoning field. Commencing with an introduction fundamentals, including theoretical foundations various cavity architectures, we discuss outcomes polariton-modified reactions. Furthermore, navigate through ongoing debates uncertainties surrounding underpinning mechanism innovative method controlling chemistry. Emphasis is placed gaining a comprehensive understanding dynamics polaritons, particular, vibrational polaritons─a pivotal facet steering Additionally, unique capability coherent two-dimensional spectroscopy dissect polariton dark mode dynamics, offering insights into critical components within that alter We further expand utility applications as well precise manipulation polarizations, notably context chiral phenomena. discussion aspires ignite deeper curiosity engagement revealing physics properties, broad fascination harnessing environments control

Language: Английский

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Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(3), P. 1214 - 1227

Published: Jan. 30, 2024

Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment polaritons requires the matter photon freedom on equal quantum mechanical footing. In limit electronic ultrastrong coupling one few molecules, it is desirable treat using tools ab initio chemistry, yielding an approach we refer cavity electrodynamics, where are treated at level electrodynamics. Here, present called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory provide ground- excited-state polaritonic surfaces with balanced description correlation effects photonic This method provides platform for electrodynamics when both electron light–matter important step toward computational approaches that yield multiple energy couplings can be leveraged dynamics simulations polariton chemistry.

Language: Английский

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Diffusion quantum Monte Carlo approach to the polaritonic ground state

Physical review. A/Physical review, A, Journal Year: 2024, Volume and Issue: 109(3)

Published: March 4, 2024

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent active fields that connects communities chemistry quantum optics. Modeling such phenomena ab initio approaches calls new methodologies, leading to reinvention many commonly used electronic structure methods, as Hartree-Fock, density functional, coupled cluster theories. In this work, we explore formally exact diffusion Monte Carlo approach obtain numerical solutions ground state during dissociation ${\mathrm{H}}_{2}$ molecular system. We examine various electron-nuclear-photon properties throughout dissociation, changes minimum cavity Born-Oppenheimer surface, localization wave function, average mode occupation. Finally, directly compare our results obtained with state-of-the-art, yet approximate, approaches.

Language: Английский

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Machine Learning for Polaritonic Chemistry: Accessing Chemical Kinetics

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5402 - 5413

Published: Feb. 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.

Language: Английский

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

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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Polariton spectra under the collective coupling regime. I. Efficient simulation of linear spectra and quantum dynamics

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(1)

Published: Jan. 7, 2025

We outline two general theoretical techniques to simulate polariton quantum dynamics and optical spectra under the collective coupling regimes described by a Holstein–Tavis–Cummings (HTC) model Hamiltonian. The first one takes advantage of sparsity HTC Hamiltonian, which allows reduce cost acting Hamiltonian onto state vector linear order number states, instead quadratic order. second is applying well-known Chebyshev series expansion approach for propagation in system; this us use much larger time step only requires few recursive operations on vectors. These approaches are can be applied any trajectory-based non-adiabatic methods. apply these with our previously developed Lindblad-partially linearized density matrix absorption system, both inhomogeneous site energy disorders dipolar orientational disorders. Our numerical results agree well previous analytic work.

Language: Английский

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Sub-bandgap charge harvesting and energy up-conversion in metal halide perovskites: ab initio quantum dynamics

npj Computational Materials, Journal Year: 2025, Volume and Issue: 11(1)

Published: Jan. 11, 2025

Metal halide perovskites (MHPs) exhibit unusual properties and complex dynamics. By combining ab initio time-dependent density functional theory, nonadiabatic molecular dynamics machine learning, we advance quantum simulation to nanosecond timescale demonstrate that large fluctuations of MHP defect energy levels extend light absorption longer wavelengths enable trapped charges escape into bands. This allows low photons contribute photocurrent through up-conversion. Deep can become shallow transiently vice versa, altering the traditional classification deep. While fluctuate more in MHPs than semiconductors, some levels, e.g., Pb interstitials, remain far from band edges, acting as charge recombination centers. Still, many defects deemed detrimental based on static structures, are fact benign The extended harvesting up-conversion provide strategies for design novel solar, optoelectronic, information devices.

Language: Английский

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Quantum Dynamics Simulations of Exciton Polariton Transport

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

Published: Jan. 21, 2025

Recent experiments have shown that exciton transport can be significantly enhanced through hybridization with confined photonic modes in a cavity. The light-matter generates exciton-polariton (EP) bands, whose group velocity is larger than the excitons. Dissipative mechanisms affect constituent states of EPs, such as exciton–phonon coupling and cavity loss, been observed to reduce velocities experiments. To elucidate impacts these dissipative on polariton transport, we developed an efficient quantum dynamics approach allows us directly simulate under collective regime beyond long-wavelength approximation. Our numerical results suggest renormalization stronger strengths smaller Q-factor. We observe transition from ballistic diffusive propagation well quality-factor-dependent behavior transient mean square displacement, agreeing recent experimental measurements.

Language: Английский

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How Quantum is the Resonance Behavior in Vibrational Polariton Chemistry?

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(36), P. 8261 - 8267

Published: Sept. 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. [

Language: Английский

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