Polariton-induced Purcell effects via a reduced semiclassical electrodynamics approach DOI

Andres Vargas,

Tao E. Li

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

Molecular Polaritons for Chemistry, Photonics and Quantum Technologies DOI Creative Commons
Bo Xiang, Wei Xiong

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

Citations

21
Diffusion quantum Monte Carlo approach to the polaritonic ground state DOI
Braden M. Weight, Sergei Tretiak, Yu Zhang

et al.

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

Citations

18
Impact of Dipole Self-Energy on Cavity-Induced Nonadiabatic Dynamics DOI
Csaba Fábri, Gábor J. Halász, Jaroslav Hofierka

et al.

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

Citations

3
Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons DOI
Tamás Szidarovszky

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

Citations

2
Collective Strong Coupling Modifies Aggregation and Solvation DOI Creative Commons
Matteo Castagnola, Tor S. Haugland, Enrico Ronca

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(5), P. 1428 - 1434

Published: Jan. 30, 2024

Intermolecular (Coulombic) interactions are pivotal for aggregation, solvation, and crystallization. We demonstrate that the collective strong coupling of several molecules to a single optical mode results in notable changes molecular excitations around perturbed molecule, thus representing an impurity otherwise ordered system. A competition between short-range coulombic long-range photonic correlations inverts local transition density polaritonic state, suggesting polarizability solvation shell. Our provide alternative perspective on recent work chemistry pave way rigorous treatment cooperative effects

Language: Английский

Citations

11
Variational Lang–Firsov Approach Plus Møller–Plesset Perturbation Theory with Applications to Ab Initio Polariton Chemistry DOI
Zhi‐Hao Cui, Arkajit Mandal, David R. Reichman

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(3), P. 1143 - 1156

Published: Feb. 1, 2024

We apply the Lang–Firsov (LF) transformation to electron–boson coupled Hamiltonians and variationally optimize parameters molecular orbital coefficients determine ground state. Møller–Plesset (MP-n, with n = 2 4) perturbation theory is then applied on top of optimized LF mean-field state improve description electron–electron correlations. The method (LF–MP) several systems, including Hubbard–Holstein model, diatomic molecule dissociation (H2, HF), modification proton transfer reactions (malonaldehyde aminopropenal) via formation polaritons in an optical cavity. show that a correction for correlation, gives quantitatively accurate energies comparable by exact diagonalization or coupled-cluster theory. effects multiple photon modes, spin polarization, comparison coherent MP are also discussed.

Language: Английский

Citations

11
Extraordinary Electrical Conductance through Amorphous Nonconducting Polymers under Vibrational Strong Coupling DOI
Sunil Kumar, Subha Biswas, Umar Rashid

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18999 - 19008

Published: May 13, 2024

Enhancing the electrical conductance through amorphous nondoped polymers is challenging. Here, we show that vibrational strong coupling (VSC) of intrinsically nonconducting and such as polystyrene, deuterated poly(benzyl methacrylate) to vacuum electromagnetic field cavity enhances conductivity by at least 6 orders magnitude compared uncoupled polymers. Remarkably, observed extraordinary mode selective occurs only under VSC aromatic C–H(D) out-of-plane bending modes The thermally activated onset becomes temperature-independent collective strength increases. characterizations are performed without external light excitation, demonstrating role field–matter in enhancing long-range transport even

Language: Английский

Citations

10
Room-temperature strong coupling between CdSe nanoplatelets and a metal–DBR Fabry–Pérot cavity DOI
Ovishek Morshed, Mitesh Amin, Nicole M. B. Cogan

et al.

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

Citations

9
Reverse Intersystem Crossing Dynamics in Vibronically Modulated Inverted Singlet–Triplet Gap System: A Wigner Phase Space Study DOI
Pijush Karak,

Pradipta Manna,

Ambar Banerjee

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(30), P. 7603 - 7609

Published: July 19, 2024

We inspect the origin of inverted singlet-triplet gap (INVEST) and slow change in reverse intersystem crossing (rISC) rate with temperature, as recently observed. A Wigner phase space study reveals that, though INVEST is found at equilibrium geometry, variation exchange interaction doubles-excitation for other geometries harmonic region leads to non-INVEST behavior. This highlights importance nuclear degrees freedom phenomenon, this case, geometric puckering studied molecule determines associated rISC dynamics.

Language: Английский

Citations

9
Simulating anharmonic vibrational polaritons beyond the long wavelength approximation DOI
Dipti Jasrasaria, Arkajit Mandal, David R. Reichman

et al.

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

Citations

1