Polariton spectra under the collective coupling regime. II. 2D non-linear spectra

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(7)

Опубликована: Фев. 20, 2025

In our previous work [Mondal et al., J. Chem. Phys. 162, 014114 (2025)], we developed several efficient computational approaches to simulate exciton–polariton dynamics described by the Holstein–Tavis–Cummings (HTC) Hamiltonian under collective coupling regime. Here, incorporated these strategies into previously Lindblad-partially linearized density matrix (L-PLDM) approach for simulating 2D electronic spectroscopy (2DES) of particular, apply quantum propagation scheme in Paper I both forward and backward propagations PLDM develop an importance sampling graphics processing unit vectorization that allow us reduce costs from O(K2)O(T3) O(K)O(T0) 2DES simulation, where K is number states T time steps propagation. We further simulated HTC regime analyzed signal rephasing non-rephasing contributions ground state bleaching, excited emission, stimulated emission pathways.

Язык: Английский

Trajectory-based non-adiabatic simulations of the polariton relaxation dynamics

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(12)

Опубликована: Март 27, 2025

We benchmark the accuracy of various trajectory-based non-adiabatic methods in simulating polariton relaxation dynamics under collective coupling regime. The Holstein–Tavis–Cummings Hamiltonian is used to describe hybrid light–matter system N molecules coupled a single cavity mode. apply recently developed simulate population by initially exciting upper state and results against populations computed from exact quantum dynamical propagation using hierarchical equations motion approach. In these benchmarks, we have systematically varied number N, detunings, strengths. Our demonstrate that symmetrical quasi-classical method with γ correction spin-mapping linearized semi-classical approaches yield more accurate than traditional mixed quantum-classical methods, such as Ehrenfest surface hopping techniques.

Язык: Английский

Theoretical Insights into the Resonant Suppression Effect in Vibrational Polariton Chemistry

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 2, 2025

Recent experiments demonstrated the possibilities of modifying ground-state chemical reaction rates by placing an ensemble molecules in optical microcavity through a resonant coupling between cavity mode and molecular vibrations. Typical VSC operate absence any light source. The VSC-induced rate constant suppression occurs under resonance condition when frequency matches vibrational frequency, only normal incidence considering in-plane momentum inside Fabry-Pérot cavity. In this work, we use quantum dynamics simulations analytic theories to provide valuable insights into observed phenomena, including behavior, nonlinear change increasing Rabi splitting, modification both reactive enthalpy entropy, reason why, with very low barrier, there is lack modification. theory also exhibits collective effects.

Язык: Английский