The experimental realization of quantum molecular spectroscopy with entangled photons remains challenging owing to the low signal-to-noise ratio resulting from the use of low-flux entangled photons. High-flux entangled photons via intense entangled beams can be used to improve the signal-to-noise ratio, but the presence of unentangled photons contaminates the quantum signal stemming from entangled photons. Here, we demonstrate how intense entangled beams can be used in multi-dimensional spectroscopy while retaining the advantage of photon entanglement. Our approach is broadly applicable to odd-ordered nonlinear spectroscopies, and it generates purely quantum spectroscopic signals. The proposed approach allows the recording of desired phase-matched signals even in a collinear beam geometry, which lifts the requirement of complicated beam geometry setups for phase matching in multi-dimensional spectroscopies.
The experimental realization of quantum molecular spectroscopy with entangled photons remains challenging owing to the low signal-to-noise ratio resulting from the use of low-flux entangled photons. High-flux entangled photons via intense entangled beams can be used to improve the signal-to-noise ratio, but the presence of unentangled photons contaminates the quantum signal stemming from entangled photons. Here, we demonstrate how intense entangled beams can be used in multi-dimensional spectroscopy while retaining the advantage of photon entanglement. Our approach is broadly applicable to odd-ordered nonlinear spectroscopies, and it generates purely quantum spectroscopic signals. The proposed approach allows the recording of desired phase-matched signals even in a collinear beam geometry, which lifts the requirement of complicated beam geometry setups for phase matching in multi-dimensional spectroscopies.
Entangled photons carry nontrivial quantum correlations that defy classical physics and provide new tools for monitoring quantum dynamics in molecules. The use of low-flux entangled photons in molecular spectroscopy has been proposed in the past to probe excited-state dynamics with enhanced temporal and spectral resolutions. However, these techniques have been challenging to implement experimentally since the resulting signal has a low signal-to-noise ratio. The signal strength can be boosted by using intense entangled-photon beams, where multiple pairs of entangled photons are present in the environment. This allows the molecule under study to interact with both entangled and unentangled photons, where the classical component of the spectroscopic signal stemming from the latter can mask the spectral features associated with the former. In this Letter, we show how the signal arising from unentangled photons can be eliminated when intense entangled-photon beams are used in two-dimensional electronic spectroscopy (2DES), and demonstrate the advantage of photonic entanglement.
Recent advances in techniques for generating quantum light have stimulated research on novel spectroscopic measurements using quantum entangled photons. One such spectroscopy technique utilizes non-classical correlations among entangled photons to enable measurements with enhanced sensitivity and selectivity. Here, we investigate the spectroscopic measurement utilizing entangled three photons. In this measurement, time-resolved entangled photon spectroscopy with monochromatic pumping [A. Ishizaki, J. Chem. Phys. 153, 051102 (2020)] is integrated with the frequency-dispersed two-photon counting technique, which suppresses undesired accidental photon counts in the detector and thus allows one to separate the weak desired signal. This time-resolved frequency-dispersed two-photon counting signal, which is a function of two frequencies, is shown to provide the same information as that of coherent two-dimensional optical spectra. The spectral distribution of the phase-matching function works as a frequency filter to selectively resolve a specific region of the two-dimensional spectra, whereas the excited-state dynamics under investigation are temporally resolved in the time region longer than the entanglement time. The signal is not subject to Fourier limitations on the joint temporal and spectral resolution, and therefore, it is expected to be useful for investigating complex molecular systems in which multiple electronic states are present within a narrow energy range.
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.
Nonlinear spectroscopy with quantum entangled photons is an emerging field of research that holds the promise to achieve superior signal-to-noise ratio and effectively isolate many-body interactions. Photon sources used for this purpose, however, lack the frequency tunability and spectral bandwidth demanded by contemporary molecular materials. Here, we present design strategies for efficient spontaneous parametric downconversion to generate biphoton states with adequate spectral bandwidth and at visible wavelengths. Importantly, we demonstrate, by suitable design of the nonlinear optical interaction, the scope to engineer the degree of spectral correlations between the photons of the pair. We also present an experimental methodology to effectively characterize such spectral correlations. Importantly, we believe that such a characterization tool can be effectively adapted as a spectroscopy platform to optically probe system-bath interactions in materials.
Optical two-dimensional coherent spectroscopy (2DCS) is a powerful ultrafast spectroscopic technique that can greatly benefit from the unique features of a femtosecond laser operating at a kHz repetition rate. However, isolating specific nonlinear signal in the collinear geometry, especially with a kHz laser, presents challenges. We present an experimental implementation of optical 2DCS in a collinear geometry using a femtosecond laser operating at a 5 KHz repetition rate. The desired nonlinear signal is selectively extracted in the frequency domain by lock-in detection. Both pump-probe and optical 2DCS experiments were conducted on a rubidium vapor. The signal-to-noise ratio of pump-probe and 2DCS spectra was characterised under various experimental parameters. The study highlights the importance of the lock-in reference frequency in overcoming the limitations imposed by low repetition rates, thereby paving the way for the application of collinear optical 2DCS in material systems requiring kHz femtosecond lasers.
Entanglement detection is one of the most conventional tasks in quantum information processing. While most experimental demonstrations of high-dimensional entanglement rely on fidelity-based witnesses, these are powerless to detect entanglement within a large class of entangled quantum states, the so-called unfaithful states. In this Letter, we introduce a highly flexible automated method to construct optimal tests for entanglement detection given a bipartite target state of arbitrary dimension, faithful or unfaithful, and a set of local measurement operators. By restricting the number or complexity of the considered measurement settings, our method outputs the most convenient protocol which can be implemented using a wide range of experimental techniques such as photons, superconducting qudits, cold atoms, or trapped ions. With an experimental quantum optics setup that can prepare and measure arbitrary high-dimensional mixed states, we implement some three-setting protocols generated by our method. These protocols allow us to experimentally certify two- and three-unfaithful entanglement in four-dimensional photonic states, some of which contain well above 50% of noise.