CUT-E as a 1/N expansion for multiscale molecular polariton dynamics DOI
Juan B. Pérez-Sánchez, Arghadip Koner, Sricharan Raghavan-Chitra

et al.

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

Quantum dynamical effects of vibrational strong coupling in chemical reactivity DOI Creative Commons
Lachlan P. Lindoy, Arkajit Mandal, David R. Reichman

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 12, 2023

Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach investigate model of cavity-modified reactions in the condensed phase. The contains coupling reaction coordinate generic solvent, cavity either or non-reactive mode, and lossy modes. Thus, many most important features needed for realistic modeling modification included. We find molecule is optical it essential treat problem mechanically obtain quantitative account alterations reactivity. sizable sharp changes rate constant associated with mechanical splittings resonances. emerge from our simulations closer those observed than previous calculations, even realistically small values loss. work highlights importance fully treatment vibrational polariton chemistry.

Language: Английский

Citations

80
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

24
Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory DOI Creative Commons
Nam Vu, Daniel Mejı́a-Rodrı́guez, Nicholas P. Bauman

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(3), P. 1214 - 1227

Published: Jan. 30, 2024

Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment polaritons requires the matter photon freedom on equal quantum mechanical footing. In limit electronic ultrastrong coupling one few molecules, it is desirable treat using tools ab initio chemistry, yielding an approach we refer cavity electrodynamics, where are treated at level electrodynamics. Here, present called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory provide ground- excited-state polaritonic surfaces with balanced description correlation effects photonic This method provides platform for electrodynamics when both electron light–matter important step toward computational approaches that yield multiple energy couplings can be leveraged dynamics simulations polariton chemistry.

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

19
Polariton spectra under the collective coupling regime. I. Efficient simulation of linear spectra and quantum dynamics DOI
M. Mondal, A. Nick Vamivakas, Steven T. Cundiff

et al.

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

Citations

5
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
Quantum Dynamics Simulations of Exciton Polariton Transport DOI Creative Commons

Benjamin X. K. Chng,

M. Mondal, Wenxiang Ying

et al.

Nano Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

Recent experiments have shown that exciton transport can be significantly enhanced through hybridization with confined photonic modes in a cavity. The light-matter generates exciton-polariton (EP) bands, whose group velocity is larger than the excitons. Dissipative mechanisms affect constituent states of EPs, such as exciton–phonon coupling and cavity loss, been observed to reduce velocities experiments. To elucidate impacts these dissipative on polariton transport, we developed an efficient quantum dynamics approach allows us directly simulate under collective regime beyond long-wavelength approximation. Our numerical results suggest renormalization stronger strengths smaller Q-factor. We observe transition from ballistic diffusive propagation well quality-factor-dependent behavior transient mean square displacement, agreeing recent experimental measurements.

Language: Английский

Citations

3
Analytic model reveals local molecular polarizability changes induced by collective strong coupling in optical cavities DOI

Jacob Horak,

Dominik Sidler, Thomas Schnappinger

et al.

Physical Review Research, Journal Year: 2025, Volume and Issue: 7(1)

Published: March 5, 2025

Despite recent numerical evidence, one of the fundamental theoretical mysteries polaritonic chemistry is how and if collective strong coupling can induce local changes electronic structure to modify chemical properties. Here we present nonperturbative analytic results for a model system consisting an ensemble N harmonic molecules under vibrational (VSC) that alters our understanding this question. By applying cavity Born-Oppenheimer partitioning on Pauli-Fierz Hamiltonian in dipole approximation, dressed many-molecule problem be solved nonperturbatively analytically dilute limit, i.e., self-consistent solution with mean-field Hartree-product wave function becomes exact. We discover molecular polarizabilities are modified even case vanishingly small single-molecule couplings. Consequently, polarization mechanism persists large-N limit. In contrast, perturbative calculation based uncoupled leads qualitatively erroneous scaling behavior vanishing effects large-N Nevertheless, exact (self-consistent) determined from simulations instead. Our observations demonstrate hitherto existing collective-scaling arguments insufficient they pave way refined single- (or few-)molecule strong-coupling systems coupling. Published by American Physical Society 2025

Language: Английский

Citations

3
How Quantum is the Resonance Behavior in Vibrational Polariton Chemistry? DOI Creative Commons
Marit R. Fiechter, Johan E. Runeson, Joseph E. Lawrence

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(36), P. 8261 - 8267

Published: Sept. 7, 2023

Recent experiments in polariton chemistry have demonstrated that reaction rates can be modified by vibrational strong coupling to an optical cavity mode. Importantly, this modification occurs only when the frequency of mode is tuned closely match a molecular frequency. This sharp resonance behavior has proved difficult capture theoretically. Only recently did Lindoy et al. [

Language: Английский

Citations

29
Theory and modeling of light-matter interactions in chemistry: current and future DOI Creative Commons
Braden M. Weight, Xinyang Li, Yu Zhang

et al.

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(46), P. 31554 - 31577

Published: Jan. 1, 2023

Light-matter interaction not only plays an instrumental role in characterizing materials' properties via various spectroscopic techniques but also provides a general strategy to manipulate material the design of novel nanostructures. This perspective summarizes recent theoretical advances modeling light-matter interactions chemistry, mainly focusing on plasmon and polariton chemistry. The former utilizes highly localized photon, plasmonic hot electrons, local heat drive chemical reactions. In contrast, chemistry modifies potential energy curvatures bare electronic systems, hence their forming hybrid states, so-called polaritons. starts with basic background interactions, molecular quantum electrodynamics theory, challenges Then, are described, future directions toward multiscale simulations interaction-mediated discussed.

Language: Английский

Citations

27