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

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Language: Английский

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

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(3)

Published: Jan. 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.

Language: Английский

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CUT-E as a 1/N expansion for multiscale molecular polariton dynamics

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(6)

Published: Feb. 10, 2025

Molecular polaritons arise when the collective coupling between an ensemble of N molecules and optical mode exceeds individual photon molecular linewidths. The complexity their description stems from multiscale nature, where local dynamics each molecule can, in principle, be influenced by behavior entire ensemble. To address this, we previously introduced a formalism called using truncated equations (CUT-E). CUT-E approaches problem two stages. First, it exploits permutational symmetries to obtain substantial simplification problem. However, this is often insufficient for parameter regimes relevant most experiments. Second, takes exact solution → ∞ limit as reference derives systematic finite-N corrections. Here, provide novel derivation based on recently developed bosonization techniques. We lay down its connections with 1/N expansions that are ubiquitous other fields physics present unexplored key aspects formalism, including various types approximations extensions high-excitation manifolds.

Language: Английский

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Simulating anharmonic vibrational polaritons beyond the long wavelength approximation

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

Published: Jan. 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.

Language: Английский

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Stochastic resonance in vibrational polariton chemistry

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(6)

Published: Feb. 10, 2025

In this work, we systematically investigate the impact of ambient noise intensity on rate modifications ground-state chemical reactions in an optical cavity under vibrational strong-coupling conditions. To achieve this, utilize a numerically exact open quantum system approach—the hierarchical equations motion twin space, combined with flexible tree tensor network state solver. Our findings reveal stochastic resonance phenomenon cavity-modified reactivities: optimal reaction enhancement occurs at intermediate level. other words, diminishes if noise, sensed by cavity–molecule through leakage, is either too weak or excessively strong. collective coupling regime, when weakly damped, strengthens as more molecules couple to cavity. contrast, strong damping, rates decline number grows.

Language: Английский

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Polariton-induced Purcell effects via a reduced semiclassical electrodynamics approach

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(12)

Published: March 24, 2025

Recent experiments have demonstrated that polariton formation provides a novel strategy for modifying local molecular processes when large ensemble of molecules is confined within an optical cavity. Herein, numerical based on coupled Maxwell–Schrödinger equations examined simulating in realistic cavity structure under collective strong coupling. In this approach, only few molecules, referred to as quantum impurities, are treated mechanically, while the remaining macroscopic layer and modeled using dielectric functions. When single electronic two-level system embedded Lorentz medium two-dimensional Bragg resonator, our simulations reveal polariton-induced Purcell effect: radiative decay rate impurity significantly enhanced by frequency matches frequency, can sometimes be greatly suppressed near resonance with bulk forming addition, approach demonstrates absorption light exhibits Rabi-splitting-dependent suppression due inclusion structure. Our also identify fundamental limitation approach—an inaccurate description dephasing rates into dark modes. This arises because dark-mode degrees freedom not explicitly included most simple As effect alters differently from weak coupling, may facilitate understanding origin polariton-modified photochemistry

Language: Английский

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Trajectory-based non-adiabatic simulations of the polariton relaxation dynamics

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(12)

Published: March 27, 2025

We benchmark the accuracy of various trajectory-based non-adiabatic methods in simulating polariton relaxation dynamics under collective coupling regime. The Holstein–Tavis–Cummings Hamiltonian is used to describe hybrid light–matter system N molecules coupled a single cavity mode. apply recently developed simulate population by initially exciting upper state and results against populations computed from exact quantum dynamical propagation using hierarchical equations motion approach. In these benchmarks, we have systematically varied number N, detunings, strengths. Our demonstrate that symmetrical quasi-classical method with γ correction spin-mapping linearized semi-classical approaches yield more accurate than traditional mixed quantum-classical methods, such as Ehrenfest surface hopping techniques.

Language: Английский

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Exploring the Delocalization of Dark States in a Multimode Optical Cavity

The Journal of Physical Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: May 20, 2025

Language: Английский

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Quantum nature of reactivity modification in vibrational polariton chemistry

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(5)

Published: Aug. 1, 2024

In this work, we present a mixed quantum–classical open quantum system dynamics method for studying rate modifications of ground-state chemical reactions in an optical cavity under vibrational strong-coupling conditions. approach, the radiation mode is treated classically with mean-field nuclear force averaging over remaining degrees freedom, both within and environment, which are handled mechanically hierarchical equations motion framework. Using conduct comparative analysis by juxtaposing results fully quantum-mechanical simulations. After eliminating spurious peaks that can occur when not using rigorous definition constant, confirm crucial role nature reproducing resonant peak observed frequency-dependent profile. other words, it appears necessary to explicitly consider quantized photonic states reactivity modification polariton chemistry (at least model systems studied work), as these phenomena stem from cavity-induced reaction pathways involving energy exchanges between photons molecular transitions.

Language: Английский

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