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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Toward Molecular Chiral Polaritons

ACS Photonics, Год журнала: 2023, Номер 10(8), С. 2440 - 2455

Опубликована: Июнь 15, 2023

Coupling between light and material excitations underlies a wide range of optical phenomena. Polaritons are eigenstates coupled system with hybridized wave function. Owing to their hybrid composition, polaritons exhibit at the same time properties typical for photonic electronic excitations, thus offering new ways controlling transport even chemical kinetics. While most theoretical experimental efforts have been focused on electric-dipole coupling matter, in chiral quantum emitters, transitions characterized by simultaneously nonzero electric magnetic dipole moments. Thus, it is natural wonder what kinds novel effects chirality may enable realm strong light–matter coupling. Right now, this field located intersection nanophotonics, optics, chemistry its infancy. In Perspective, we offer our view toward polaritons. We review basic physical concepts underlying matter electromagnetic field, discuss main challenges that need be solved, consider could enabled matter.

Язык: Английский

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Computational study on the catalytic control of endo/exo Diels-Alder reactions by cavity quantum vacuum fluctuations

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Май 13, 2023

Achieving control over chemical reaction's rate and stereoselectivity realizes one of the Holy Grails in chemistry that can revolutionize pharmaceutical industries. Strong light-matter interaction optical or nanoplasmonic cavities might provide knob to reach such control. In this work, we demonstrate catalytic selectivity an cavity for two selected Diels-Alder cycloaddition reactions using quantum electrodynamics coupled cluster (QED-CC) method. Herein, find by changing molecular orientation with respect polarization mode be significantly inhibited selectively enhanced produce major endo exo products on demand. This work highlights potential utilizing vacuum fluctuations modulate achieve a practical non-intrusive way. We expect present findings will applicable larger set relevant reactions, including click reactions.

Язык: Английский

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Strong Coupling in Chiral Cavities: Nonperturbative Framework for Enantiomer Discrimination

Physical Review X, Год журнала: 2023, Номер 13(3)

Опубликована: Июль 7, 2023

Strongly coupling chiral molecules to circularly polarized light in an optical cavity give the two mirror-image forms of these different energies, suggesting a viable way differentiate between them.

Язык: Английский

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Chiral Polaritonics: Analytical Solutions, Intuition, and Use

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(15), С. 3777 - 3784

Опубликована: Апрель 13, 2023

Preferential selection of a given enantiomer over its chiral counterpart becomes increasingly relevant in the advent next era medical drug design. In parallel, cavity quantum electrodynamics has grown into solid framework to control energy transfer and chemical reactivity. this work, we derive an analytical solution system many emitters interacting with -- analogy widely used Tavis-Cummings Hopfield models optics. We are able estimate discriminating strength polaritonics, discuss possible future development directions, exciting applications such as elucidating homochirality, deliver much needed intuition foster freshly flourishing field polaritonics.

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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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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Ab Initio Calculations of Quantum Light–Matter Interactions in General Electromagnetic Environments

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(2), С. 926 - 936

Опубликована: Янв. 8, 2024

The emerging field of strongly coupled light–matter systems has drawn significant attention in recent years because the prospect altering both physical and chemical properties molecules materials. Because this draws on ideas from condensed-matter physics quantum optics, it attracted theoreticians fields. While former often employ accurate descriptions electronic structure matter, description electromagnetic environment is oversimplified. In contrast, latter employs sophisticated while using oversimplified few-level approximations structure. Both approaches are problematic system incapable describing effects such as light-induced structural changes system, environments can lead to unphysical predictions interactions strengths misrepresented. work, we overcome these shortcomings present first method which quantitatively describe general principles. We realize by combining macroscopic QED (MQED) with Quantum Electrodynamical Density-Functional Theory. To exemplify approach, consider example an absorbing spherical cavity study impact different parameters transition weak-to-strong coupling for aromatic molecules. As part also provide easy-to-use tool calculate simple setups. Our work a step toward parameter-free ab initio calculations will help bridge gap between theoretical methods experiments field.

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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Blackbody Radiation and Thermal Effects on Chemical Reactions and Phase Transitions in Cavities

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

An important question in polariton chemistry is whether reacting molecules are thermal equilibrium with their surroundings. If not, can experimental changes observed reaction rates of a cavity (even without optical pumping) be attributed to higher/lower temperature inside the cavity? In this work, we address by computing differences between and air outside. We found difference negligible for most reactions. On other hand, phase transitions cavities, as material actively maintained heating/cooling source experiments, show that cavities modify transition temperatures when mirrors windows ideal (nonabsorbing); however, modification vanishes real used. This conclusion relies on having low contact resistance molecules. Finally, find substantial blackbody spectral energy density free space infrared which reveal resonance effects could potentially play role explaining chemical reactivity dark.

Язык: Английский

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