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arXiv:2511.01723

Spontaneous Raman Scattering under Vibrational Strong Coupling: The Critical Role of Polariton Spatial Mode Coherence

Maxime Dherbécourt, Joël Bellessa, Clémentine Symonds, Guillaume Weick, David Hagenmüller

cond-mat.mes-hallquant-phSubmitted Nov 3, 2025• Announced Nov 4, 2025• Revised Sep 9, 2026 (v2)
v1 · Nov 3, 2025v2 · Sep 9, 2026
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Abstract

Resonant coupling of a vibration to a cavity mode has been reported to dramatically modify spontaneous Raman scattering, but subsequent studies have produced conflicting results. In this Letter, we develop a microscopic quantum framework that captures the spatial structure of polaritonic modes. In a homogeneously filled cavity, spatial overlap between polaritons and cavity resonances enforces selection rules that suppress the initially reported polaritonic Raman peaks, consistent with most experiments. In contrast, for a quasi-two-dimensional (2D) molecular layer, these rules are lifted, yielding Raman peaks at the polariton energies. Our Letter clarifies that the Raman response under vibrational strong coupling is determined by cavity-vibration spatial mode overlap and offers a framework for Raman studies of strongly coupled quasi-2D systems.

Journal reference
Phys. Rev. Lett. 137, 116901 (2026)
DOI
10.1103/m138-4w64

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Resonant coupling of a vibration to a cavity mode has been reported to dramatically modify spontaneous Raman scattering, but subsequent studies have produced conflicting results. In this Letter, we develop a microscopic quantum framework that captures the spatial structure of polaritonic modes. In a homogeneously filled cavity, spatial overlap between polaritons and cavity resonances enforces selection rules that suppress the initially reported polaritonic Raman peaks, consistent with most experiments. In contrast, for a quasi-two-dimensional (2D) molecular layer, these rules are lifted, yielding Raman peaks at the polariton energies. Our Letter clarifies that the Raman response under vibrational strong coupling is determined by cavity-vibration spatial mode overlap and offers a framework for Raman studies of strongly coupled quasi-2D systems.
Molecular strong coupling offers exciting prospects in physics, chemistry and materials science. Whilst attention has been focused on developing realistic models for the molecular systems, the important role played by the entire photonic mode structure of the optical cavities has been less explored. We show that the effectiveness of molecular strong coupling may be critically dependent on cavity finesse. Specifically we only see emission associated with a dispersive lower polariton for cavities with sufficient finesse. By developing an analytical model of cavity photoluminescence in a multimode structure we clarify the role of finite-finesse in polariton formation, and show that lowering the finesse reduces the extent of the mixing of light and matter in polariton states. We suggest that the detailed nature of the photonic modes supported by a cavity will be as important in developing a coherent framework for molecular strong coupling as the inclusion of realistic molecular models.
Stimulated Raman scattering is conventionally employed to probe vibrational dynamics by inducing a coherent oscillation within a molecular ensemble. In contrast, spontaneous Raman scattering is considered as an incoherent process because the scattered field lacks any predictable phase relationship with the incoming laser pulse. It raises questions about the nature of the quantum state of a molecular ensemble following spontaneous Stokes scattering: should it be described as a statistical mixture of vibrationally excited molecules, where collective coherence is absent? Here, we measure time-resolved Stokes--anti-Stokes two-photon coincidences on a molecular liquid and find that a coherent superposition of two collective vibrational modes from two isotopic sub-ensembles is generated under spontaneous Raman scattering. Our results confirm that a spatially extended vibrational coherence emerges when a single collective excitation is spontaneously scattered and detected in a single spatiotemporal mode.
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.
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We show that spontaneous Raman scattering of incident radiation can be observed in cavity-QED systems without external enhancement or coupling to any vibrational degree of freedom. Raman scattering processes can be evidenced as resonances in the emission spectrum, which become clearly visible as the cavity-QED system approaches the ultrastrong coupling regime. We provide a quantum mechanical description of the effect, and show that ultrastrong light-matter coupling is a necessary condition for the observation of Raman scattering. This effect, and its strong sensitivity to the system parameters, opens new avenues for the characterization of cavity QED setups and the generation of quantum states of light
We show that spontaneous Raman scattering of incident radiation can be observed in cavity-QED systems without external enhancement or coupling to any vibrational degree of freedom. Raman scattering processes can be evidenced as resonances in the emission spectrum, which become clearly visible as the cavity-QED system approaches the ultrastrong coupling regime. We provide a quantum mechanical description of the effect, and show that ultrastrong light-matter coupling is a necessary condition for the observation of Raman scattering. This effect, and its strong sensitivity to the system parameters, opens new avenues for the characterization of cavity QED setups and the generation of quantum states of light.