Cavity Quantum Electrodynamics Enables para- and ortho-Selective Electrophilic Bromination of Nitrobenzene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16184 - 16193

Published: May 30, 2024

Coupling molecules to a quantized radiation field inside an optical cavity has shown great promise modify chemical reactivity. In this work, we show that the ground-state selectivity of electrophilic bromination nitrobenzene can be fundamentally changed by strongly coupling reaction cavity, generating ortho- or para-substituted products instead meta product. Importantly, these are not obtained from same outside cavity. A recently developed ab initio approach was used theoretically compute relative energies cationic Wheland intermediates, which indicate kinetically preferred site for all products. Performing analysis electron density intermediates and demonstrate how strong induces reorganization molecular charge distribution, in turn leads different sites directly dependent on conditions. Overall, results presented here understand induced changes reactivity mechanistic perspective as well connect frontier theoretical simulations state-of-the-art, but realistic, experimental

Language: Английский

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Strong coupling-induced frequency shifts of highly detuned photonic modes in multimode cavities

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(20)

Published: May 28, 2024

Strong coupling between light and molecules is a fascinating topic exploring the implications of hybridization photonic molecular states. For example, many recent experiments have explored possibility that strong vibrational modes might modify chemical reaction rates. In these experiments, reactants are introduced into planar cavity, mode bond strongly couples to one supported by cavity. Some quantify rates tracking spectral shift higher-order cavity highly detuned from reactant. Here, we show position modes, even though they detuned, can still be influenced coupling. We highlight need consider this coupling-induced frequency if avoid underestimating cavity-induced rate changes. anticipate our work will assist in re-analysis several high-profile results has for design future experiments.

Language: Английский

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Room-temperature strong coupling between CdSe nanoplatelets and a metal–DBR Fabry–Pérot cavity

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(1)

Published: July 2, 2024

The generation of exciton–polaritons through strong light–matter interactions represents an emerging platform for exploring quantum phenomena. A significant challenge in colloidal nanocrystal-based polaritonic systems is the ability to operate at room temperature with high fidelity. Here, we demonstrate room-temperature coupling CdSe nanoplatelets (NPLs) a Fabry–Pérot optical cavity, leading Rabi splitting 74.6 meV. Quantum–classical calculations accurately predict complex dynamics between many dark state excitons and optically allowed polariton states, including experimentally observed lower photoluminescence emission, concentration intensities higher in-plane momenta as cavity becomes more negatively detuned. measured 5 K similar that 300 K, validating feasibility temperature-independent operation this system. Overall, these results show NPLs are excellent material facilitate development technologies.

Language: Английский

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i-PI 3.0: A flexible and efficient framework for advanced atomistic simulations

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(6)

Published: Aug. 14, 2024

Atomic-scale simulations have progressed tremendously over the past decade, largely thanks to availability of machine-learning interatomic potentials. These potentials combine accuracy electronic structure calculations with ability reach extensive length and time scales. The i-PI package facilitates integrating latest developments in this field advanced modeling techniques a modular software architecture based on inter-process communication through socket interface. choice Python for implementation rapid prototyping but can add computational overhead. In new release, we carefully benchmarked optimized several common simulation scenarios, making such overhead negligible when is used model systems up tens thousands atoms using widely adopted machine learning potentials, as Behler–Parinello, DeePMD, MACE neural networks. We also present features, including an efficient algorithm bosonic fermionic exchange, framework uncertainty quantification be conjunction infrastructure that allows deeper integration electronic-driven simulations, approach simulate coupled photon-nuclear dynamics optical or plasmonic cavities.

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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