CUT-E as a 1/N expansion for multiscale molecular polariton dynamics

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

Опубликована: Фев. 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.

Язык: Английский

Semiclassical Truncated-Wigner-Approximation Theory of Molecular Exciton-Polariton Dynamics in Optical Cavities

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

Molecular exciton polaritons, hybrid states formed through the strong coupling of molecular electronic excitations with optical cavity modes, offer a powerful avenue for controlling photophysical and photochemical processes in systems. Here, we present semiclassical framework investigating dynamics polaritons using truncated Wigner approximation (TWA). This approach extends prior TWA method developed vibration-polariton ( J. Chem. Theory Comput. 2024, 20, 3019–3027) by incorporating treatment quantum coherence between ground excited states. To validate framework, first apply it to simplified system two-level (spin-1/2) molecules without vibronic coupling, demonstrating agreement fully simulations systems large ensemble. We further extend model include revealing dynamic polaron decoupling effect, where persists under light–matter coupling. These findings provide critical insights into collective behavior preservation polaritonic implications designing cavity-mediated processes.

Язык: Английский

Sympathetic Mechanism for Vibrational Condensation Enabled by Polariton Optomechanical Interaction

Physical Review Letters, Год журнала: 2024, Номер 133(18)

Опубликована: Окт. 29, 2024

We demonstrate a macrocoherent regime in exciton-polariton systems, where nonequilibrium polariton Bose-Einstein condensation coexists with macroscopically occupied vibrational states. Strong exciton-vibration coupling induces an effective optomechanical interaction between cavity polaritons and degrees of freedom molecules, leading to amplification resonant blue-detuned configuration. This provides sympathetic mechanism achieve potential applications cavity-controlled chemistry, nonlinear, quantum optics.

Язык: Английский