Quantum optical fields offer numerous control knobs which are not available with classical light and may be used for monitoring the properties of matter by novel types of spectroscopy. It has been recently argued that such quantum spectroscopy signals can be obtained by a simple averaging of their classical spectroscopy counterparts over the Glauber-Sudarshan quasiprobability distribution of the quantum field; the quantum light thus merely provides a novel gating window for the classical response functions. We show that this argument only applies to the linear response and breaks down in the nonlinear regime. The quantum response carries additional valuable information about response and spontaneous fluctuations of matter that may not be retrieved from the classical response by simple data processing. This is connected to the lack of a nonlinear fluctuation-dissipation relation.
Quantum optical fields offer numerous control knobs which are not available with classical light and may be used for monitoring the properties of matter by novel types of spectroscopy. It has been recently argued that such quantum spectroscopy signals can be obtained by a simple averaging of their classical spectroscopy counterparts over the Glauber-Sudarshan quasiprobability distribution of the quantum field; the quantum light thus merely provides a novel gating window for the classical response functions. We show that this argument only applies to the linear response and breaks down in the nonlinear regime. The quantum response carries additional valuable information about response and spontaneous fluctuations of matter that may not be retrieved from the classical response by simple data processing. This is connected to the lack of a nonlinear fluctuation-dissipation relation.
In a recent paper [Phys. Rev. A 91, 053844 (2015)], Mukamel and Dorfman compare spectroscopies performed with classical vs quantum light and conclude that nonlinear quantum-spectroscopy signals cannot be obtained from averaging their classical-spectroscopy counterparts over the Glauber-Sudarshan quasiprobability distribution of the quantum field. In this Comment, we show that this interpretation is correct only when classical spectroscopy is perceived as a theoretical description which neglects quantum fluctuations of light altogether. While such an assumption can be a good approximation and useful for comparing theoretical results, it is never realized exactly in laser-spectroscopy experiments that typically use coherent states. Even though coherent states represent the most classical form of light, their quantumness must be considered to fully understand laser-spectroscopy experiments and their connection to quantum spectroscopy, performed with true quantum sources, such as Schr\"odinger's cat states. Thus, instead of using a classical approximation, the connection between coherent states and true quantum states of light must be considered. We rigorously show that quantum spectroscopy can always be projected from the experimentally realized coherent-state spectroscopy regardless how nonlinear the system response is.
We discuss the proper definition of the term ``quantum spectroscopy.'' Since the response of matter to coherent states of the field is not necessarily classical, positivity of the Glauber-Sudarshan P representation as used by Kira et al. [Nat. Phys. 7, 799 (2011)] does not imply that the response is classical. We show that classical and quantum spectroscopies may be unambiguously distinguished by formulating the signals in terms of multipoint field correlation functions.
Abstract Conventional spectroscopy uses classical light to detect matter properties through the variation of its response with frequencies or time delays. Quantum light opens up new avenues for spectroscopy by utilizing parameters of the quantum state of light as novel control knobs and through the variation of photon statistics by coupling to matter. This Roadmap article focuses on using quantum light as a powerful sensing and spectroscopic tool to reveal novel information about complex molecules that is not accessible by classical light. It aims at bridging the quantum optics and spectroscopy communities which normally have opposite goals: manipulating complex light states with simple matter e.g. qubits versus studying complex molecules with simple classical light, respectively. Articles cover advances in the generation and manipulation of state-of-the-art quantum light sources along with applications to sensing, spectroscopy, imaging and interferometry.
For decades, ultrafast light-matter interactions have provided a powerful means to observe electrons in motion across a wide range of physical systems. This dissertation builds new theoretical frameworks to make sense of the emergent phenomena that arise when light drives matter into the strong-field regime, spanning atomic, molecular, and condensed-matter systems. The resulting dynamics leave their fingerprints on a variety of observables, such as photoionization spectra, high-harmonic generation, and nonlinear spectroscopic signals, each of which provides a different window onto the underlying electronic motion. The work is organized into two parts.The first part focuses on the electric-field observables of nonlinear optical signals. Because both the amplitude and phase of the emitted field are experimentally accessible through techniques such as spectral interferometry and electro-optic sampling, the full field itself serves as a rich observable for characterizing nonlinear responses in atomic, molecular, and condensed-matter systems. Leveraging this, the simulations presented here uncover novel and largely unexplored physical phenomena encoded in these field observables. The second part turns to optical spectroscopy with quantum light. Although nonlinear optical processes are conventionally modeled within a semiclassical framework, treating the matter quantum mechanically while the driving ultrafast fields remain classical, the resulting signals can nonetheless exhibit intrinsically non-classical properties. Building on this insight, a framework for interpreting experimental data is introduced and used to show that four-wave mixing driven by ultrafast femtosecond laser pulses generates bright squeezed light. Beyond squeezed light, strong field-matter interactions can also produce attosecond entangled photons, a distinct form of quantum light. Several strategies are proposed to enhance the efficiency of their generation, with the developed theory predicting rates of energy-time entangled biphoton production orders of magnitude beyond those achievable with conventional spontaneous parametric down-conversion (SPDC) sources. The studies presented here are initial steps toward investigating quantum properties of these systems through quantum phynonlinear spectroscopy, which is not achievable with classical light.
We survey the inclusion of interferometric elements in nonlinear spectroscopy performed with quantum light. Controlled interference of electromagnetic fields coupled to matter can induce constructive or destructive contributions of microscopic coupling sequences (histories) of matter. Since quantum fields do not commute, quantum light signals are sensitive to the order of light-matter coupling sequences. Matter correlation functions are thus imprinted by different field factors, which depend on that order. We identify the associated quantum information obtained by controlling the weights of different contributing pathways and offer several experimental schemes for recovering it. Nonlinear quantum response functions include out-of-time-ordering matter correlators (OTOCs), which reveal how perturbations spread throughout a quantum system (information scrambling). Their effect becomes most notable when using ultrafast pulse sequences with respect to the path difference induced by the interferometer. OTOCs appear in quantum-informatics studies in other fields, including black hole, high energy, and condensed matter physics.
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.