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Abstract Pathway selectivity in quantum spectroscopy with entangled photons is a powerful spectroscopic tool. Phase‐matched signals involving classical light contain contributions from multiple material pathways, whereas quantum spectroscopy may allow the selection of individual pathways. 2D electronic‐vibrational spectroscopy (2DEVS) is a four‐wave mixing technique which employs visible and infrared entangled photons. It is showed how the three contributing pathways—ground state bleach, excited state absorption, and excited state emission—can be separated by photon‐number‐resolved coincidence measurements. Entangled photons thus reveal spectral features not visible in the classical signal, with an enhanced spectral resolution. 

Abstract Ultrafast reactions activated by light absorption are governed by multidimensional excited-state (ES) potential energy surfaces (PESs), which describe how the molecular potential varies with the nuclear coordinates. ES PESs ad-hoc displaced with respect to the ground state can drive subtle structural rearrangements, accompanying molecular biological activity and regulating physical/chemical properties. Such displacements are encoded in the Franck-Condon overlap integrals, which in turn determine the resonant Raman response. Conventional spectroscopic approaches only access their absolute value, and hence cannot determine the sense of ES displacements. Here, we introduce a two-color broadband impulsive Raman experimental scheme, to directly measure complex Raman excitation profiles along desired normal modes. The key to achieve this task is in the signal linear dependence on the Frank-Condon overlaps, brought about by non-degenerate resonant probe and off-resonant pump pulses, which ultimately enables time-domain sensitivity to the phase of the stimulated vibrational coherences. Our results provide the tool to determine the magnitude and the sensed direction of ES displacements, unambiguously relating them to the ground state eigenvectors reference frame. 

The development of experimental techniques at the nanoscale has enabled the performance of spectroscopic measurements on single-molecule current-carrying junctions. These experiments serve as a natural intersection for the research fields of optical spectroscopy and molecular electronics. We present a pedagogical comparison between the perturbation theory expansion of standard nonlinear optical spectroscopy and the (non-self-consistent) perturbative diagrammatic formulation of the nonequilibrium Green’s functions method (which is widely used in molecular electronics), highlighting their similarities and differences. By comparing the two approaches, we argue that the optical spectroscopy of open quantum systems must be analyzed within the more general Green’s function framework. 

We study entanglement created between two isolated qubits by interaction with entangled-photon pairs obtained by parametric down-conversion of a laser pump field. The induced entanglement is quantified using the mixed state Concurrence proposed by Wootters et al. [Phys. Rev. Lett. 78, 5022 (1997)]. A universal value of qubit-entanglement, which is independent on the photon-pair wavefunction is identified to leading order in the qubit–field interaction and the pump field amplitude. The qubit entanglement decreases at higher laser pump intensities due to interference between the entangled photon pairs, which creates excitations in the qubit system. Maximal Concurrence is produced by only generating coherences between the ground and the highest excited qubit states.