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arXiv:2607.12676

Entanglement and Optical Nonreciprocity in spontaneous Raman Scattering

Frank Schlawin

quant-phphysics.chem-phSubmitted Jul 14, 2026• Announced Jul 15, 2026• 0 citations
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Abstract

Inelastic light scattering is a central tool for sample characterization and label-free imaging across the physical and life sciences. Recent work has suggested that scattered light can also exhibit nonclassical correlations. Here, we develop a microscopic theory of Raman scattering that connects naturally to established descriptions of entangled-photon generation in three- and four-wave mixing, while capturing essential differences arising from the resonant, dissipative character of Raman scattering. Using a cumulant-expansion approach, we analyze the entanglement structure of the scattered sidebands and identify signatures that distinguish Raman-mediated correlations from those generated in conventional off-resonant nonlinear wave mixing. In particular, we show that Raman scattering induces chiral couplings between Stokes and anti-Stokes sidebands, leading to nonreciprocal amplification of coherent seed fields. These results establish a theoretical framework for Raman-based quantum photonic protocols and suggest routes toward quantum-enhanced Raman spectroscopy and imaging.

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Inelastic light scattering is a central tool for sample characterization and label-free imaging across the physical and life sciences. Recent work has suggested that scattered light can also exhibit nonclassical correlations. Here, we develop a microscopic theory of Raman scattering that connects naturally to established descriptions of entangled-photon generation in three- and four-wave mixing, while capturing essential differences arising from the resonant, dissipative character of Raman scattering. Using a cumulant-expansion approach, we analyze the entanglement structure of the scattered sidebands and identify signatures that distinguish Raman-mediated correlations from those generated in conventional off-resonant nonlinear wave mixing. In particular, we show that Raman scattering induces chiral couplings between Stokes and anti-Stokes sidebands, leading to nonreciprocal amplification of coherent seed fields. These results establish a theoretical framework for Raman-based quantum photonic protocols and suggest routes toward quantum-enhanced Raman spectroscopy and imaging.
The process in which Raman scattering produces correlated Stokes and anti‐Stokes radiation is known as Stokes–anti‐Stokes (SaS) scattering. It has been shown recently that this process can generate entangled photon pairs, making it a promising tool for quantum optical technologies, but a proper quantum theoretical description was lacking. In this article, a fully quantum derivation of the electric polarization in a medium with vibrational Raman response, with quantized electromagnetic fields, is developed. Using quantum perturbation theory for Heisenberg operators, the solution for the material electric polarization is found and it is shown that a four‐wave mixing‐like correlated SaS scattering appears in the first order of perturbation and completely characterizes the nonresonant SaS photon pair production. It is also discussed how to construct the third‐order nonlinear optical susceptibility for the SaS scattering from the quantum formalism and show that it coincides with the one derived for classical fields in stimulated Raman.
Quantum correlations offer the possibility of surpassing classical limits in optical measurements, but their integration into nonlinear vibrational spectroscopy has remained largely unexplored. Here, we introduce a quantum-enhanced implementation of coherent Raman spectroscopy that employs broadband squeezed-light detection to interrogate relative intensity correlations between Stokes and anti-Stokes fields generated in an ultrafast four-wave-mixing process. By exploiting nonclassical correlations between these fields, we suppress the nonresonant background and enhance the signal-to-noise performance in both temporal and spectral domains, enabling detection sensitivities beyond the classical shot-noise limit. Importantly, the quantum advantage demonstrated here does not arise solely from improved detection statistics. Rather, it originates from microscopic intermolecular correlations mediated by cascaded exchange of a virtual photon between molecular pairs. This mechanism establishes a fundamentally distinct and significant pathway for information extraction in vibrational spectroscopy, providing access to structural and dynamical observables that are intrinsically inaccessible by conventional classical Raman techniques. Numerical simulations illustrate the power of the technique by resolving intradimer [Formula: see text] bond splitting in cyclobutane thymine dimers following ultraviolet excitation, highlighting its potential for probing ultrafast photochemical processes with quantum-limited sensitivity and for label-free biomedical optical sensing and imaging.
It is known that spontaneous Raman scattering is accompanied by the appearance of nonclassical cross correlations of photons at Stokes and anti-Stokes frequencies. Such correlations occur due to the internal nonlinear interaction between electronic and nuclear vibration degrees of freedom. Since the properties of a given media are unchangeable, the possibilities for controlling the cross correlations are limited. This, in turn, restricts the possible applications of the correlated light obtained during the spontaneous Raman scattering. In this work, we investigate the influence of statistical properties of an incident light on the cross correlations of Stokes and anti-Stokes light. We show that the incoherence of the incident light results not only in the incoherence of the scattered light but also in the enhancement of the interbeam coherence at different frequencies. We demonstrate that the cross correlations of Stokes and anti-Stokes light intensities are enhanced when the incident light with high second-order autocorrelation function is applied. Our results pave the way to control correlated light obtained in the process of spontaneous Raman scattering.
Spontaneous vibrational Raman scattering is a ubiquitous form of light-matter interaction whose description necessitates quantization of the electromagnetic field. It is usually considered as an incoherent process because the scattered field lacks any predictable phase relationship with the incoming field. When probing an ensemble of molecules, the question therefore arises: What quantum state should be used to describe the molecular ensemble following spontaneous Stokes scattering? We experimentally address this question by measuring time-resolved Stokes-anti-Stokes two-photon coincidences on a molecular liquid consisting of several sub-ensembles with slightly different vibrational frequencies. When spontaneously scattered Stokes photons and subsequent anti-Stokes photons are detected into a single spatiotemporal mode, the observed dynamics is inconsistent with a statistical mixture of individually excited molecules. Instead, we show that the data are reproduced if Stokes-anti-Stokes correlations are mediated by a collective vibrational quantum, i.e. a coherent superposition of all molecules interacting with light. Our results demonstrate that the degree of coherence in the vibrational state of the liquid is not an intrinsic property of the material system, but rather depends on the optical excitation and detection geometry.
With the development of quantum optics, photon correlations acquired a prominent role as a tool to test our understanding of physics, and played a key role in verifying the validity of quantum mechanics. The spatial and temporal correlations in a light field also reveal information about its origin, and allow us to probe the nature of the physical systems interacting with it. Additionally, with the advent of quantum technologies, they have acquired technological relevance, as they are expected to play an important role in quantum communication and quantum information processing. This thesis develops techniques that combine spontaneous Raman scattering with Time Correlated Single Photon Counting, and uses them to study the quantum mechanical nature of high frequency vibrations in crystals and molecules. We demonstrate photon bunching in the Stokes and anti-Stokes fields scattered from two ultrafast laser pulses, and use their cross-correlation to measure the 3.9 ps decay time of the optical phonon in diamond. We then employ this method to measure molecular vibrations in CS2, where we are able to excite the respective vibrational modes of the two isotopic species present in the sample in a coherent superposition, and observe quantum beating between the two signals. Stokes scattering, when combined with a projective measurement, leads to a well defined quantum state. We demonstrate this by measuring the second order correlation function of the anti-Stokes field conditional on detecting one or more photons in the Stokes field, which allows us to observe a phonon modeâ s transition form a thermal state into the first excited Fock state, and measure its decay over the characteristic phonon lifetime. Finally, we use this technique to prepare a highly entangled photon-phonon state, which violates a Bell-type inequality. We measure S = 2.360 ± 0.025, violating the CHSH inequality, compatible with the non-locality of the state. The techniques we developed open the door to the study of a broad range of physical systems, where spectroscopic information is obtained with the preparation of specific quantum states. They also hold potential for future technological use, and promote vibrational Raman scattering to a resource in nonlinear quantum optics -- where it used to be considered as a source of noise instead.
Statistical properties of light produced in spontaneous Raman scattering on an ensemble of molecules indicate the quantum nature of this phenomenon. The scattered light is non-classical and has high non-classical intensity correlations between Stokes and anti-Stokes components. The temporal coherence of this light is well investigated, while many questions related to spatial coherence remain open. Recent experiments reveal two peculiar features of the spatial coherence of the Stokes and anti-Stokes light. First, the intensity correlations between Stokes and anti-Stokes light remain non-classical even for macroscopic samples containing many molecules. Second, these correlations decrease when signal propagates through a multi-mode optical fiber: the more propagating fiber modes at Stokes and anti-Stokes frequencies the less the correlations. Moreover, the second-order autocorrelation function of Stokes and anti-Stokes light also decreases with the number of propagating modes in multi-mode fiber. In this paper, we build a model of spontaneous Raman scattering correlations of light produced by an ensemble of molecules and propagating through weakly guiding optical fiber that quantitatively explains all these observations. We show that spacial orthogonality of the fiber modes makes the light propagating through these modes uncorrelated in the standard detection scheme. This leads to suppression of non-classical intensity correlations of the total field in the multi-mode fiber. We find the degree of non-classical correlations on fiber parameters. The obtained results pave the way for engineering of non-classical Stokes -- anti-Stokes correlations.