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arXiv:2609.38533

Input-output formulation of quantum light spectroscopy

Liwen Ko, Robert L. Cook, K. Birgitta Whaley

quant-phphysics.chem-phphysics.opticsSubmitted Sep 29, 2026• Announced Oct 1, 2026• 0 citations
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Abstract

We develop an input-output formulation of quantum light spectroscopy (QLS) by combining the input-output theory, commonly used in quantum optics, with the perturbative expansion method for nonlinear spectroscopy, commonly used in chemical physics. The use of the input-output relation provides physical intuition for how matter systems alter the photon input field. As examples, we consider linear spectroscopy, fluorescence, intra-beam $G^{(2)}$, and Hong-Ou-Mandel correlation. For certain initial photon states, we show that signal expectation values can be evaluated non-perturbatively. For general initial photon states, the signals can be computed via a perturbative expansion of the input-output relation. The input-output relation reduces the work needed to perturbatively expand the optical signal, allowing for cleaner derivations and clearer physical interpretations.

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We develop an input-output formulation of quantum light spectroscopy (QLS) by combining the input-output theory, commonly used in quantum optics, with the perturbative expansion method for nonlinear spectroscopy, commonly used in chemical physics. The use of the input-output relation provides physical intuition for how matter systems alter the photon input field. As examples, we consider linear spectroscopy, fluorescence, intra-beam G(2)G^{(2)}G(2), and Hong-Ou-Mandel correlation. For certain initial photon states, we show that signal expectation values can be evaluated non-perturbatively. For general initial photon states, the signals can be computed via a perturbative expansion of the input-output relation. The input-output relation reduces the work needed to perturbatively expand the optical signal, allowing for cleaner derivations and clearer physical interpretations.
Spectroscopy based on individual-photon-level light sources brings new variables to both spectroscopy and imaging. We refer to this approach as quantum-light spectroscopy (QLS). The photon statistics of different types of photon sources and photon entanglements are briefly described. We then illustrate the potential of QLS by means of some current experimental examples including time-resolved spectroscopy performed with single photons and quantum-enhanced optical imaging, showing how all the methods rely on correlations between entangled photons in the pair. We then ask: how might physical chemists exploit QLSs to expose new physical insights? For example, can we address fundamental questions in interactions between light and molecules or materials that are very difficult to address with classical light sources? Does QLS open up techniques to study highly congested spectra with higher combined spectral and temporal resolution than is possible with classical light? The concept of QLS also opens the potential study of fundamental questions such as what initial excited states are produced by individual photon absorption? We also point out the experimental challenges in extending QLS to more complex spectroscopies, such as multidimensional spectroscopies. We conclude with a brief selection of recent theoretical proposals to extend the capabilities of the QLS.
The purpose of this paper is to extend linear systems and signals theory to include single photon quantum signals. We provide detailed results describing how quantum linear systems respond to multichannel single photon quantum signals. In particular, we characterize the class of states (which we call photon-Gaussian states) that result when multichannel photons are input to a quantum linear system. We show that this class of quantum states is preserved by quantum linear systems. Multichannel photon-Gaussian states are defined via the action of certain creation and annihilation operators on Gaussian states. Our results show how the output states are determined from the input states through a pair of transfer function relations. We also provide equations from which output signal intensities can be computed. Examples from quantum optics are provided to illustrate the results.
= 0, 1, 2, ··· classical light pulses and an entangled photon pair (a biphoton state) where one photon acts as a reference without interacting with the matter sample, identical signals can be obtained by replacing the biphotons with classical-like coherent states of light, where these are defined explicitly in terms of the parameters of the biphoton states. An input-output formulation of quantum nonlinear spectroscopy is used to prove this equivalence. We demonstrate the equivalence numerically by comparing a classical pump-quantum probe experiment with the corresponding classical pump-classical probe experiment. This analysis shows that understanding the equivalence between entangled biphoton probes and carefully designed classical-like coherent state probes leads to quantum-inspired classical experiments that yield equivalent signals and provides insights for the future design of QLS experiments that could provide a true quantum advantage.
The application of quantum states of light such as entangled photons, for example, created by parametric down conversion, has experienced tremendous progress in the almost 40 years since their first experimental realization. Initially, they were employed in the investigation of the foundations of quantum physics, such as the violation of Bell's inequalities and studies of quantum entanglement. They later emerged as basic platforms for quantum communication protocols and, in the recent experiments on single-photon interactions, in photonic quantum computation. These applications aim at the controlled manipulation of the photonic degrees of freedom, and therefore rely on simple models of matter, where the analysis is simpler. Furthermore, quantum imaging with entangled light can achieve enhanced resolution, and quantum metrology can overcome the shot noise limit for classical light. This Account focuses on an entirely different emerging class of applications using quantum light as a powerful spectroscopic tool to reveal novel information about complex molecules. These applications utilize two appealing properties of quantum light: its distinct intensity fluctuations and its nonclassical bandwidth properties. These give rise to new and surprising behavior of nonlinear optical signals. Nonclassical intensity fluctuations can enhance nonlinear optical signals relative to linear absorption. For instance, the two-photon absorption of entangled photon pairs scales linearly (rather than quadratically) in the photon flux, just like a single photon absorption. This enables nonlinear quantum spectroscopy of photosensitive, for example, biological, samples at low light intensities. We will discuss how the two-photon absorption cross section becomes a function of the photonic quantum state, which can be manipulated by properties of the entangled photon pairs. In addition, the quantum correlations in entangled photon states further influence the nonlinear signals in a variety of ways. Apart from affecting the signal's scaling with intensity, they also constitute an entirely new approach to shaping and controlling excitation pathways in molecular aggregates in a way that cannot be achieved with shaped classical pulses. This is because between the two absorption events in entangled two-photon absorption, the light and material system are entangled. Classical constraints for the simultaneous time and frequency resolution can thus be circumvented, since the two are not Fourier conjugates. Here we review the simplest manifestation of quantum light spectroscopy, two-photon absorption spectroscopy with entangled photons. This will allow us to discuss exemplarily the impact of quantum properties of light on a nonlinear optical signal and explore the opportunities for future applications.
Conspectus The enhanced interest in quantum-related phenomena has provided new opportunities for chemists to push the limits of detection and analysis of chemical processes. As some have called this the second quantum revolution, a time has come to apply the rules learned from previous research in quantum phenomena toward new methods and technologies important to chemists. While there has been great interest recently in quantum information science (QIS), the quest to understand how nonclassical states of light interact with matter has been ongoing for more than two decades. Our entry into this field started around this time with the use of materials to produce nonclassical states of light. Here, the process of multiphoton absorption led to photon-number squeezed states of light, where the photon statistics are sub-Poissonian. In addition to the great interest in generating squeezed states of light, there was also interest in the formation of entangled states of light. While much of the effort is still in foundational physics, there are numerous new avenues as to how quantum entanglement can be applied to spectroscopy, imaging, and sensing. These opportunities could have a large impact on the chemical community for a broad spectrum of applications. In this Account, we discuss the use of entangled (or quantum) light for spectroscopy as well as applications in microscopy and interferometry. The potential benefits of the use of quantum light are discussed in detail. From the first experiments in porphyrin dendrimer systems by Dr. Dong-Ik Lee in our group to the measurements of the entangled two photon absorption cross sections of biological systems such as flavoproteins, the usefulness of entangled light for spectroscopy has been illustrated. These early measurements led the way to more advanced measurements of the unique characteristics of both entangled light and the entangled photon absorption cross-section, which provides new control knobs for manipulating excited states in molecules. The first reports of fluorescence-induced entangled processes were in organic chromophores where the entangled photon cross-section was measured. These results would later have widespread impact in applications such as entangled two-photon microscopy. From our design, construction and implementation of a quantum entangled photon excited microscope, important imaging capabilities were achieved at an unprecedented low excitation intensity of 10 7 photons/s, which is 6 orders of magnitude lower than the excitation level for the classical two-photon image. New reports have also illustrated an advantage of nonclassical light in Raman imaging as well. From a standpoint of more precise measurements, the use of entangled photons in quantum interferometry may offer new opportunities for chemistry research. Experiments that combine molecular spectroscopy and quantum interferometry, by utilizing the correlations of entangled photons in a Hong–Ou–Mandel (HOM) interferometer, have been carried out. The initial experiment showed that the HOM signal is sensitive to the presence of a resonant organic sample placed in one arm of the interferometer. In addition, parameters such as the dephasing time have been obtained with the opportunity for even more advanced phenomenology in the future.
Entangled photon pairs have been used for molecular spectroscopy in the form of entangled two-photon absorption and in quantum interferometry for precise measurements of light source properties and time delays. We present an experiment that combines molecular spectroscopy and quantum interferometry by utilizing the correlations of entangled photons in a Hong-Ou-Mandel (HOM) interferometer to study molecular properties. We find that the HOM signal is sensitive to the presence of a resonant organic sample placed in one arm of the interferometer, and the resulting signal contains information pertaining to the light-matter interaction. We can extract the dephasing time of the coherent response induced by the excitation on a femtosecond time scale. A dephasing time of 102 fs is obtained, which is relatively short compared to times found with similar methods and considering line width broadening and the instrument entanglement time As the measurement is done with coincidence counts as opposed to simply intensity, it is unaffected by even-order dispersion effects, and because interactions with the molecular state affect the photon correlation, the observed measurement contains only these effects and no other classical losses. The experiments are accompanied by theory that predicts the observed temporal shift and captures the entangled photon joint spectral amplitude and the molecule's transmission in the coincidence counting rate. Thus, we present a proof-of-concept experimental method based of entangled photon interferometry that can be used to characterize optical properties in organic molecules and can in the future be expanded on for more complex spectroscopic studies of nonlinear optical properties.