In this paper the two-photon absorption by a molecule is studied when photons are prepared in a high-dimension entangled state. The light field is prepared in a spatial two-photon qudit state and its interaction with a molecule shows new interference effects observed in the calculated absorption cross-section. Oscillations in the absorption cross-section demonstrate its dependence on the path phases of the two-qudit state. The two-photon absorption cross-section is dependent on the dimension of the two-qudit photonic state.
In this paper the two-photon absorption by a molecule is studied when photons are prepared in a high-dimension entangled state. The light field is prepared in a spatial two-photon qudit state and its interaction with a molecule shows new interference effects observed in the calculated absorption cross-section. Oscillations in the absorption cross-section demonstrate its dependence on the path phases of the two-qudit state. The two-photon absorption cross-section is dependent on the dimension of the two-qudit photonic state.
We review recent theoretical and experimental works where are proposed and demonstrated how to use photon pairs created by spontaneous parametric down-conversion to generate entangled states of D-dimensional quantum systems, or qudits. This is the first demonstration of high-dimensional entanglement based on the intrinsic transverse momentum entanglement of the type-II down-converted photons. The qudit space is defined by an aperture made up of an opaque screen with D slits (paths), placed in the arms of the twin photons. By manipulating the pump beam profile we can prepare different entangled states of these possible paths. We focus our attention on an important case for applications in quantum information: the maximally entangled states. Experimental results for qudits with D=4 and D=8 are shown and measuring a two-photon conditional interference, we also demonstrate the nonclassical character of the correlations.
Quantum light spectroscopy, providing novel molecular information non-accessible by classical light, necessitates new computational tools when applied for complex molecular systems. We introduce two computational protocols for the molecular nuclear wave packet dynamics interacting with an entangled photon pair to produce the entangled two-photon absorption signal. The first involves summing over transition pathways in a temporal grid defined by two light-matter interaction times accompanied by the field correlation functions of quantum light. The signal is obtained by averaging over the two-time distribution characteristic of the entangled photon state. The other protocol involves a Schmidt decomposition of the entangled light and requires summing over the Schmidt modes. We demonstrate how photon entanglement can be used to control and manipulate the two-photon excited nuclear wave packets in a displaced harmonic oscillator model.
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.
Quantum light spectroscopy, providing novel molecular information nonaccessible by classical light, necessitates new computational tools when applied to complex molecular systems. We introduce two computational protocols for the molecular nuclear wave packet dynamics interacting with an entangled photon pair to produce an entangled two-photon absorption signal. The first involves summing over transition pathways in a temporal grid defined by two light-matter interaction times accompanied by the field correlation functions of quantum light. The signal is obtained by averaging over the two time distribution characteristics of the entangled photon state. The other protocol involves a Schmidt decomposition of the entangled light and requires summing over the Schmidt modes. We demonstrate how photon entanglement can be used to control and manipulate the two-photon excited nuclear wave packets in a displaced harmonic oscillator model.
We propose and analyze a scheme for controlling coherent photon transmission and reflection in a cavity-quantum-electrodynamics (CQED) system consisting of an optical resonator coupled with three-level atoms coherently prepared by a control laser from free space. When the control laser is off and the cavity is excited by two identical light fields from two ends of the cavity, the two input light fields can be completely absorbed by the CQED system and the light energy is converted into the excitation of the polariton states, but no light can escape from the cavity. Two distinct cases of controlling the perfect photon absorption are analyzed: (a) when the control laser is tuned to the atomic resonance and creates electromagnetically induced transparency, the perfect photon absorption is suppressed and the input light fields are nearly completely transmitted through the cavity; (b) when the control laser is tuned to the polariton state resonance and inhibits the polariton state excitation, the perfect photon absorption is again suppressed and the input light fields are nearly completely reflected from the cavity. Thus, the CQED system can act as a perfect absorber or near-perfect transmitter and/or reflector by simply turning the control laser off or on. Such interference control of the coherent photon-atom interaction in the CQED system should be useful for a variety of applications in optical logical devices.
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.