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arXiv:2604.18456

Disorder-induced non-Gaussian states in large ensembles of cavity-coupled molecules

R. Schwengelbeck, M. Pandini, R. Daraban, J. Schachenmayer

quant-phphysics.chem-phSubmitted Apr 20, 2026• Announced Apr 21, 2026
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Abstract

We analyze vibrational dynamics in a toy model for polaritonic chemistry under collective electronic strong coupling. In a Holstein-Tavis-Cummings model, incoherently excited by a photon, we show that disorder leads to non-Gaussian states of vibrational modes on short time scales at the single-molecule level. Using exact matrix product state simulations, we demonstrate that this effect can remain robust for larger molecule numbers, implying that nuclear wave packets cannot be effectively described by thermal states. Furthermore, we compare simulations of the exact quantum dynamics with semiclassical approximations. We find that the Ehrenfest approximation can only well reproduce ensemble-averaged observables for very large system sizes. Also simulations in the truncated Wigner approximation fail to capture the non-Gaussian effects. Our work highlights the importance of disorder and genuine quantum effects in cavity-modified nuclear dynamics in polaritonic chemistry.

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We analyze vibrational dynamics in a toy model for polaritonic chemistry under collective electronic strong coupling. In a Holstein-Tavis-Cummings model, incoherently excited by a photon, we show that disorder leads to non-Gaussian states of vibrational modes on short time scales at the single-molecule level. Using exact matrix product state simulations, we demonstrate that this effect can remain robust for larger molecule numbers, implying that nuclear wave packets cannot be effectively described by thermal states. Furthermore, we compare simulations of the exact quantum dynamics with semiclassical approximations. We find that the Ehrenfest approximation can only well reproduce ensemble-averaged observables for very large system sizes. Also simulations in the truncated Wigner approximation fail to capture the non-Gaussian effects. Our work highlights the importance of disorder and genuine quantum effects in cavity-modified nuclear dynamics in polaritonic chemistry.
The field of Polaritonic Chemistry studies molecules strongly coupled to the light field of optical cavities. The resulting modification of the potential energy landscape has been demonstrated to enable control over the chemical and physical properties of materials and molecular ensembles. This thesis extends the Tavis–Cummings model to describe molecules under strong light–matter coupling, incorporating static dipole moments and dipole self-energy contributions derived from the Pauli–Fierz Hamiltonian. These additional terms are shown to be essential for reproducing cavity-modified molecular dynamics and spectra. Simulations on the nuclear wavefunction propagation of MgH+ molecules demonstrate the impact of these terms, while an effective two-level system model accurately captures the behavior of large ensembles. Beyond single excitations, the thesis also explores the higher excitation manifolds of the Tavis-Cummings model, which reveals that allowing for more than a single excitation makes the reaction of the involved polaritons entropically more favorable. Open-system simulations highlight how the coherence of the system's initial state governs decay pathways and enables long-lived energy storage. Finally, a multilevel vibrational model coupled to a two-mode cavity is introduced, where a Raman scheme enables selective mixing of vibrational states. The simulation results show that continuous pumping can drive molecules into specific vibrational states while suppressing electronic excitation, both for single molecules and small ensembles. Together, these results provide new theoretical insights into the mechanisms by which optical cavities reshape molecular energy landscapes. The results suggest approaches for controlling photonic, electronic, and vibrational dynamics in strongly coupled systems, contributing to the theoretical foundation of polariton chemistry.
Vibrational strong coupling (VSC), the strong coupling between a Fabry-Perrot cavity and molecular vibrations at mid-infrared frequencies, has received important attention in the last years due to its capacity of modifying both vibrational spectra and chemical reactivity. VSC is a collective effect, and in this work, we introduce Path Integral Monte Carlo (PIMC) simulations that not only take into account the quantum character of the molecular vibrations and of the optical resonance of the cavity but also reproduce this collective behavior by considering multiple replicas of the molecular system. Moreover, we show that it is possible to extract from the PIMC simulations the decomposition of the hybrid optical and molecular states in terms of the bare molecular modes. On a model system of an ensemble of disordered Morse oscillators coupled to a single cavity through the Pauli-Fierz Hamiltonian, PIMC can retrieve known features obtained from analytical modes such as the Tavis-Cummings model and obtain a very close agreement with exact diagonalization for a small number of Morse oscillators. We also find that notwithstanding the anhamonic character of the Morse oscillators, the collective mode coupled to the cavity behaves as a harmonic oscillator, following the quantum central limit theorem.
An empirical framework for studying the way vacuum fluctuations in a Fabry–Perot cavity produce collective light–matter hybrid states (polariton states) is reported. The reason that the Tavis–Cummings model, where a single mode of the radiation field couples to all the molecules, succeeds is discussed in terms of the strong phase correlation of the vacuum fluctuations in the cavity, which produces a single effective cavity mode (ECM). The model is used to study the onset of the collective state, or “superradiant phase”, for ensembles of molecules with significant disorder in their transition energies, as a function of cavity strength factor, from low Q cavities to high Q cavities. A key result is the quantification of the coherence of the ensemble of the lowest energy eigenstate. This is assessed, primarily, using an entropy distance measure. The statistical model provides a physical intuition for the formation of coherence of polariton states when the collective coupling is strong enough that they dominate over the tail of the dark-state density-of-states.
Davydov trial states, in combination with the Green's function method, we study the dynamics of the Tavis-Cummings model and the Holstein-Tavis-Cummings model in the presence of diagonal disorder and cavity-qubit coupling disorder. For the Tavis-Cummings model, time evolution of the photon population, the optical absorption spectra, and the hetero-entanglement between the qubits and the cavity mode are calculated by using the Green's function method to corroborate numerically exact results of Davydov's Ansätze. For the Holstein-Tavis-Cummings model, only the latter is utilized to simulate effects of disorder on the photon population dynamics and the absorption spectra. We have demonstrated that the complementary employment of analytical and numerical methods permits uncovering a fairly comprehensive picture of a variety of complex behaviors in disordered multidimensional polaritonic cavity quantum electrodynamics systems.
Strong coupling of organic molecules to the vacuum field of a nanoscale cavity can be used to modify their chemical and physical properties. We extend the Tavis-Cummings model for molecular ensembles and show that the often neglected interaction terms arising from the static dipole moment and the dipole self-energy are essential for a correct description of the light-matter interaction in polaritonic chemistry. On the basis of a full quantum description, we simulate the excited-state dynamics and spectroscopy of MgH+ molecules resonantly coupled to an optical cavity. We show that the inclusion of static dipole moments and the dipole self-energy is necessary to obtain a consistent model. We construct an efficient two-level system approach that reproduces the main features of the real molecular system and may be used to simulate larger molecular ensembles.
The demonstration of strong and ultrastrong coupling regimes of cavity QED with polyatomic molecules has opened new routes to control chemical dynamics at the nanoscale. We show that strong resonant coupling of a cavity field with an electronic transition can effectively decouple collective electronic and nuclear degrees of freedom in a disordered molecular ensemble, even for molecules with high-frequency quantum vibrational modes having strong electron-vibration interactions. This type of polaron decoupling can be used to control chemical reactions. We show that the rate of electron transfer reactions in a cavity can be orders of magnitude larger than in free space for a wide class of organic molecular species.