Polariton spectra under the collective coupling regime. I. Efficient simulation of linear spectra and quantum dynamics

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

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Quantum Dynamics Simulations of Exciton Polariton Transport

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

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Efficient formulation of multitime generalized quantum master equations: Taming the cost of simulating 2D spectra

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(4)

Published: Jan. 25, 2024

Modern 4-wave mixing spectroscopies are expensive to obtain experimentally and computationally. In certain cases, the unfavorable scaling of quantum dynamics problems can be improved using a generalized master equation (GQME) approach. However, inclusion multiple (light–matter) interactions complicates motion leads seemingly unavoidable cubic in time. this paper, we present formulation that greatly simplifies reduces computational cost previous work extended GQME framework treat arbitrary numbers measurements. Specifically, remove time derivatives correlation functions from modified Mori–Nakajima–Zwanzig by switching discrete-convolution implementation inspired transfer tensor We then demonstrate method’s capabilities simulating 2D electronic spectra for excitation-energy-transfer dimer model. our method, resolution data arbitrarily coarsened, especially along t2 axis, which mirrors how obtained experimentally. Even modest case, demands O(103) fewer points. further able decompose into one-, two-, three-time correlations, showing when system enters Markovian regime where measurements unnecessary predict future becomes quadratic. This offers ability generate long-time only short-time data, enabling access timescales previously beyond reach standard methodologies.

Language: Английский

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

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(7)

Published: Feb. 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.

Language: Английский

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Ab Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(24), P. 9278 - 9289

Published: Dec. 12, 2023

Recent experiments have revealed the profound effect of strong light-matter interactions in optical cavities on electronic ground state molecular systems. This phenomenon, known as vibrational coupling, can modify reaction rates and induce formation polaritons, hybrid states involving both photon modes, modes molecules. We present an ab initio methodology based cavity Born-Oppenheimer Hartree-Fock ansatz, which is specifically powerful for ensembles molecules, to calculate vibro-polaritonic IR spectra. method allows a comprehensive analysis these states. Our semiclassical approach, validated against full quantum simulations, reproduces key features The underlying analytic gradients also allow optimization cavity-coupled systems performing dynamics simulations.

Language: Английский

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Coherent multidimensional spectroscopy in polariton systems

Physical review. A/Physical review, A, Journal Year: 2024, Volume and Issue: 109(6)

Published: June 11, 2024

The fast dynamics of molecular polaritonics is scrutinized theoretically through the implementation two-dimensional spectroscopy protocols. We derive conceptually simple and computationally efficient formulas to calculate spectra for molecules, each them modeled as a system two electronic states including vibrational relaxation, immersed in an optical cavity, thus coupled quantized radiation. Cavity photon losses relaxation are incorporated into Hamiltonian form open quantum that solved master equation. In collective case, dark revealed be crucial factor explain asymmetries both diagonal cross peaks long waiting times between excitation detection, feature shown by recent experiments. Our theoretical method provides deeper insight those processes yield relevant signals multidimensional spectroscopy.

Language: Английский

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Theory and quantum dynamics simulations of exciton-polariton motional narrowing

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

Published: Aug. 9, 2024

The motional narrowing effect has been extensively studied for cavity exciton–polariton systems in recent decades both experimentally and theoretically, which is featured by (1) the subaverage behavior (2) asymmetric linewidths upper polariton lower polariton. However, a minimal theoretical model that clear adequate to address all these effects as well linewidth scaling relations remains missing. In this work, based on single mode 1D Holstein–Tavis–Cummings (HTC) model, we of linear absorption spectra via semi-analytic derivations numerically exact quantum dynamics simulations using hierarchical equations motion approach. results reveal under collective light–matter coupling between N molecules, scales 1/N slow limit, while fast due polaron decoupling effect. Furthermore, varying detunings, exhibit significant narrowing, covering characters mentioned above. Our analytic expressions [Eqs. (34) (35)] agree with numerical parameter regimes explored. These indicate physics adequately accounted single-mode HTC model. We envision expression presented work will offer great value providing better understanding

Language: Английский

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Non-equilibrium rate theory for polariton relaxation dynamics

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(10)

Published: Sept. 13, 2024

We derive an analytic expression of the non-equilibrium Fermi’s golden rule (NE-FGR) for a Holstein–Tavis–Cumming Hamiltonian, universal model many molecules collectively coupled to optical cavity. These NE-FGR expressions capture full-time-dependent behavior rate constant transitions from polariton states dark states. The is shown be reduced well-known frequency domain-based equilibrium (E-FGR) in and collective limit retain same scaling with number sites non-collective cases. use these perform population dynamics time-non-local time-local quantum master equation obtain accurate initially occupied upper or lower Furthermore, significantly improves accuracy when starting compared E-FGR theory, highlighting importance non-Markovian short-time transient transition constant.

Language: Английский

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Mechanism of Molecular Polariton Decoherence in the Collective Light–Matter Couplings Regime

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(47), P. 11773 - 11783

Published: Nov. 18, 2024

Molecular polaritons, the hybridization of electronic states in molecules with photonic excitation inside a cavity, play an important role fundamental quantum science and technology. Understanding decoherence mechanism molecular polaritons is among most significant questions. We theoretically demonstrate that hybridizing many excitons cavity protects overall coherence from phonon-induced decoherence. The polariton time can be prolonged up to 100 fs realistic collective Rabi splitting quality factor at room temperature, compared typical which around 15 fs. Our numerically exact simulations analytic theory suggest dominant population transfer upper state dark manifold. Increasing coupling strength will increase energy gap between these two sets thus prolong lifetime. further derived valuable scaling relations directly indicate how depends on number molecules, splittings, light–matter detunings.

Language: Английский

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Ab initio spin-mapping non-adiabatic dynamics simulations of photochemistry

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(8)

Published: Feb. 25, 2025

We perform on-the-fly non-adiabatic molecular dynamics simulations using the recently developed spin-mapping formalism. Two quantum approaches based on this mapping formalism, (i) fully linearized Spin-LSC and (ii) partially Spin-PLDM, are explored quasi-diabatic propagation scheme. have performed in four ab initio models for which benchmark multiple spawning (AIMS) data been published. find that spin-LSC previously reported symmetric quasi-classical (SQC) provide nearly equivalent population dynamics. While we expected more involved spin-PLDM method to superior accuracy compared other mapping-based approaches, SQC spin-LSC, found it with AIMS results. further explore underpinnings of correlation function by decomposing its N2 density matrix-focused initial conditions, where N is number states subsystem. Finally, an approximate form function, simplifies simulation reduces computational costs from N.

Language: Английский

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