Quantum nature of reactivity modification in vibrational polariton chemistry

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(5)

Опубликована: Авг. 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.

Язык: Английский

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Stochastic resonance in vibrational polariton chemistry

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(6)

Опубликована: Фев. 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.

Язык: Английский

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Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction

Physical Review Letters, Год журнала: 2025, Номер 134(22)

Опубликована: Июнь 2, 2025

We address the challenge of incorporating non-Markovian electronic friction effects in quantum-mechanical approximations dynamical observables. A generalized Langevin equation is formulated for ring-polymer molecular dynamics rate calculations, which combines with a description nuclear quantum adsorbates on metal surfaces. An efficient propagation algorithm introduced that captures both spatial dependence strength and frictional memory. This framework applied to model hydrogen diffusing Cu(111) derived from density functional theory revealing significant alterations constants tunneling crossover temperatures due effects. Our findings explain why previous classical simulations Markovian showed unexpectedly good agreement experiment, highlighting critical role first-principles atomistic simulations. Published by American Physical Society 2025

Язык: Английский

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Phase space perspective on a model for isomerization in an optical cavity

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(7)

Опубликована: Авг. 18, 2023

Explanation for the modification of rates and mechanism reactions carried out in optical cavities still eludes us. Several studies indicate that cavity-mediated changes nature vibrational energy flow within a molecule may play significant role. Here, we study model polaritonic system, proposed analyzed earlier by Fischer et al., J. Chem. Phys. 156, 154305 (2022), comprising one-dimensional isomerization mode coupled to single photon lossless cavity. We show probability presence virtual photons, specific cavity-system coupling strengths cavity frequencies, can exhibit suppression or enhancement different choices initial reactant vibropolariton wavepacket. observe qualitative agreement between classical quantum average probabilities case. A part effects due be rationalized terms "chaos-order-chaos" transition phase space localization polariton states dominantly participate dynamics. On other hand, with zero photons (i.e., "dark cavity"), is suppressed when frequency tuned near fundamental reactive mode. The classical-quantum correspondence case unsatisfactory. In this simple model, find arises interplay dynamics tunneling.

Язык: Английский

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Quantum nature of reactivity modification in vibrational polariton chemistry

Опубликована: Май 29, 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 mechanical simulations. Through comparison, confirm crucial role nature reproducing resonant peak observed frequency-dependent profile. other words, it to explicitly consider quantized photonic states reactivity modification polariton chemistry, as these phenomena stem from cavity-induced reaction pathways involving energy exchanges between photons molecular transitions.

Язык: Английский

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Exact factorization of the photon–electron–nuclear wavefunction: Formulation and coupled-trajectory dynamics

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(8)

Опубликована: Авг. 27, 2024

We employ the exact-factorization formalism to study coupled dynamics of photons, electrons, and nuclei at quantum mechanical level, proposing illustrative examples model situations nonadiabatic spontaneous emission electron–nuclear systems in regime strong light–matter coupling. make a particular choice factorization for such multi-component system, where full wavefunction is factored as conditional electronic amplitude marginal photon–nuclear amplitude. Then, we apply coupled-trajectory mixed quantum–classical (CTMQC) algorithm perform trajectory-based simulations, by treating photonic nuclear degrees freedom on equal footing terms classical-like trajectories. The analysis time-dependent potentials theory along with assessment performance CTMQC allows us point out some limitations current approximations used CTMQC. Meanwhile, comparing other algorithms, namely multi-trajectory Ehrenfest Tully surface hopping, demonstrates better quality predictions.

Язык: Английский

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Simulations of photoinduced processes with the exact factorization: State of the art and perspectives

Physical Chemistry Chemical Physics, Год журнала: 2024, Номер 26(42), С. 26693 - 26718

Опубликована: Янв. 1, 2024

This perspective offers an overview of the applications exact factorization electron-nuclear wavefunction in simulations ultrafast processes molecules with main focus on photochemistry.

Язык: Английский

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Resonance Theory and Quantum Dynamics Simulations of Vibrational Polariton Chemistry

Опубликована: Май 29, 2023

We present numerically exact quantum dynamics simulations using the hierarchical equation of motion (HEOM) 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 (RPV) mode" enhances steady-state population excited states, leading an enhanced product at resonant condition, when frequency matches transition frequency. Based on numerical observations, we analytic rate theory explain observed sharp peak profile tuning match ground state states. This further explains origin broadening profile. Both constant and simulation predict VSC-modified will change quadratically as light-matter strength increases this effect magnify lifetime increases. To best our knowledge, is first able behavior adiabatic reaction cavity. envision it offer invaluable theoretical insights unravel mysteries experimentally coupling-induced modification.

Язык: Английский

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Resonance Theory and Quantum Dynamics Simulations of Vibrational Polariton Chemistry

Опубликована: Июль 18, 2023

We present numerically exact quantum dynamics simulations using the hierarchical equation of motion (HEOM) 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 (RPV) 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 coupling-induced modifications

Язык: Английский

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Resonance Theory of Vibrational Polariton Chemistry at the Normal Incidence

Опубликована: Окт. 12, 2023

We present a theory that explains the reso- nance 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)]. Us- ing Fermi’s golden rule (FGR), we formulate this many molecules inside FP microcavity. The clearly ex- plains resonance condition observed VSC and provides theoretical explanation why only incident angle there effect, whereas an oblique incidence, no apparent even though both cases generate Rabi splitting forming polariton states.

Язык: Английский

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