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Shaul Mukamel

Publications and source records attributed to Shaul Mukamel.

At least 37 records · Page 2Linked to original sources
arXiv2021

Distinguishability and "which pathway" information in multidimensional interferometric spectroscopy with a single entangled photon-pair

Correlated photons inspire abundance of metrology-related platforms, which benefit from quantum (anti-) correlations and outperform their classical-light counterparts. While such demonstrations mainly focus on entanglement, the role of photon exchange-phase and degree of distinguishability have not been widely utilized in quantum-enhanced applications. Using an interferometric setup we show that even at low degree entanglement, when a two-photon wave-function is coupled to matter, it is encoded with a reliable "which pathway?" information. An interferometric exchange-phase-cycling protocol is developed, which enables phase-sensitive discrimination between microscopic interaction histories (pathways). We find that quantum-light interferometry facilitates utterly different set of time-delay variables, which are unbound by uncertainty to the inverse bandwidth of the wave-packet. We illustrate our findings on an exciton model-system, and demonstrate how to probe intraband dephasing in time-domain without temporal resolution at the detection. The exotic scaling of multiphoton coincidence with respect to the applied intensity is discussed.

quant-ph↗
arXiv2021

Interferometric-Spectroscopy With Quantum-Light; Revealing Out-of-Time-Ordering Correlators

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 sequence. 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 (OTOC) 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. OTOC appear in quantum-informatics studies in other fields, including black holes, high energy, and condensed matter physics.

quant-ph↗
arXiv2021

Heisenberg-Uncertainty of Spatially-Gated Electromagnetic Fields

A Heisenberg uncertainty relation is derived for spatially-gated electric and magnetic field fluctuations. The uncertainty increases for small gating sizes which implies that in confined spaces the quantum nature of the electromagnetic field must be taken into account. Optimizing the state of light to minimize the electric at the expense of the magnetic field, and vice versa should be possible. Spatial confinements and quantum fields may alternatively be realized without gating by interaction of the field with a nanostructure. Possible applications include nonlinear spectroscopy of nanostructures and optical cavities and chiral signals.

quant-ph↗
arXiv2021

Quantum susceptibilities in time-domain sampling of electric field fluctuations

Electro-optic sampling has emerged as a new quantum technique enabling measurements of electric field fluctuations on subcycle time scales. Probing a second-order nonlinear material with an ultrashort coherent laser pulse imprints the fluctuations of a terahertz field onto the resulting near-infrared electrooptic signal. We describe how the statistics of this time-domain signal can be calculated theoretically, incorporating from the onset the quantum nature of the electric fields involved in the underlying interactions. To this end, a microscopic quantum theory of the electro-optic process is developed using an ensemble of non-interacting three-level systems as a model for the nonlinear material. We find that the response of the nonlinear medium can be separated into a classical part sampling the terahertz field and quantum contributions independent of the state of the probed terahertz field. The quantum response is caused by interactions between the three-level systems mediated by the terahertz vacuum fluctuations. It arises due to cascading processes and contributions described by quantum susceptibilities solely accessible via quantum light. We show that the quantum contributions can be substantial and might even dominate the total response. We also determine the conditions under which the classical response serves as a good approximation of the electro-optic process and demonstrate how the statistics of the sampled terahertz field can be reconstructed from the statistics of the electro-optic signal. In a complementary regime, electro-optic sampling can serve as a spectroscopic tool to study the pure quantum susceptibilities of materials.

quant-ph↗
arXiv2021

Hong-Ou-Mandel interferometry and spectroscopy using entangled photons

Optical interferometry has been a long-standing setup for characterization of quantum states of light. Both the linear and the nonlinear interferences can provide information about the light statistics an underlying detail of the light-matter interactions. Here we demonstrate how interferometric detection of nonlinear spectroscopic signals may be used to improve the measurement accuracy of matter susceptibilities. Light-matter interactions change the photon statistics of quantum light, which are encoded in the field correlation functions. Application is made to the Hong-Ou-Mandel two-photon interferometer that reveals entanglement-enhanced resolution that can be achieved with existing optical technology.

quant-ph↗
arXiv2021

Manipulating Core-Excitations in Molecules by X-ray Cavities

Core-excitations on different atoms are highly localized and therefore decoupled. By placing molecules in an X-ray cavity the core-transitions become coupled via the exchange of cavity photons and form delocalized hybrid light-matter excitations known as core-polaritons. We demonstrate these effects for the two inequivalent carbon atoms in 1,1-difluoroethylene. Polariton signatures in the X-ray absorption, two-photon absorption, and multidimensional four-wave mixing, signals are predicted.

quant-ph↗
arXiv2021

High temporal and spectral resolution of stimulated x-ray Raman signals with stochastic free-electron-laser pulses

The chaotic nature of x-ray free-electron-laser pulses is a major bottleneck that has limited the joint temporal and spectral resolution of spectroscopic measurements. We show how to use the stochastic x-ray field statistics to overcome this difficulty by correlation signals averaged over independent pulse realizations. No control is required over the spectral phase of the pulse, enabling immediate application with existing, noisy x-ray free-electron-laser pulses. The proposed stimulated Raman technique provides the broad observation bandwidth and high time-frequency resolution needed for the observation of elementary molecular events. A model is used to simulate chaotic free-electron-laser pulses and calculate their correlation properties. The resulting joint temporal/spectral resolution is exemplified for a molecular model system with time-dependent frequencies and for the RNA base Uracil passing through a conical intersection. Ultrafast coherences, which represent a direct signature of the nonadiabatic dynamics, are resolved. The detail and depth of physical information accessed by the proposed stochastic signal are virtually identical to those obtained by phase-controlled pulses.

physics.optics↗
arXiv2020

Element- and enantiomer-selective visualization of ibuprofen dimer vibrations

In chemistry, biology and materials science, the ability to access interatomic interactions and their dynamical evolution has become possible with the advent of femtosecond lasers. In particular, the observation of vibrational wave packets via optical (UV-visible-IR) spectroscopies has been a major achievement as it can track the motion of nuclei within the system. However, optical spectroscopies only detect the effect of the interatomic vibrations on the global electronic surfaces. New tuneable, pulsed and polarized sources of short-wavelength radiation, such as X-Ray Free electron lasers, can overcome this limitation, allowing for chemical and, of primary importance in biochemistry, enantiomeric selectivity. This selectivity may be complemented by taking into account the chemical shifts of atoms belonging to different molecular moieties

cond-mat.soft↗
arXiv2020

Visualizing Conical Intersection Passages via Vibronic Coherence Maps Generated by Stimulated Ultrafast X--Ray Raman Signals

The rates and outcomes of virtually all photophysical and photochemical processes are determined by Conical Intersections. These are regions of degeneracy between electronic states on the nuclear landscape of molecules where electrons and nuclei evolve on comparable timescales and become strongly coupled, enabling radiationless relaxation channels upon optical excitation. Due to their ultrafast nature and vast complexity, monitoring Conical Intersections experimentally is an open challenge. We present a simulation study on the ultrafast photorelaxation of uracil, which demonstrates a new window into Conical Intersections obtained by recording the transient wavepacket coherence during this passage with an x-ray free electron laser pulse. We report two major findings. First, we find that the vibronic coherence at the conical intersection lives for several hundred femtoseconds and can be measured during this entire time. Second, the time-dependent energy splitting landscape of the participating vibrational and electronic states is directly extracted from Wigner spectrograms of the signal. These offer a novel physical picture of the quantum Conical Intersection pathways through visualizing their transient vibronic coherence distributions. The path of a nuclear wavepacket around the Conical Intersection is directly mapped by the proposed experiment.

physics.chem-ph↗
arXiv2020

Chiral Four-Wave-Mixing signals with circularly-polarized X-ray pulses

Chiral four-wave-mixing signals are calculated using the irreducible tensor formalism. Different polarization and crossing angle configurations allow to single out the magnetic dipole and the electric quadrupole interactions. Other configurations can reveal that the chiral interaction occurs at a given step within the nonlinear interaction pathways contributing to the signal. Applications are made to the study of valence excitations of S-ibuprofen by chiral Stimulated X-ray Raman signals at the Carbon K-edge and by chiral visible 2D Electronic Spectroscopy.teraction pathways contributing to the signal.

physics.chem-ph↗
arXiv2019

Scattering-based geometric shaping of photon-photon interactions

We construct an effective Hamiltonian of interacting bosons, based on scattered radiation off vibrational modes of designed molecular architectures. Making use of the infinite yet countable set of spatial modes representing the scattering of light, we obtain a variable photon-photon interaction in this basis. The effective Hamiltonian hermiticity is controlled by a geometric factor set by the overlaps of spatial modes. Using this mapping, we relate intensity measurements of the light to correlation functions of the interacting bosons evolving according to the effective Hamiltonian, rendering local as well as nonlocal observables accessible. This architecture may be used to simulate the dynamics of interacting bosons, as well as designing tool for multi-qubit photonic gates in quantum computing applications. Variable hopping, interaction and confinement of the active space of the bosons are demonstrated on a model system.

quant-ph↗
arXiv2019

Flux-conserving diagrammatic formulation of optical spectroscopy of open quantum systems

We present a theoretical approach to optical spectroscopy of open nonequilibrium systems, which generalizes traditional nonlinear optical spectroscopy tools by imposing charge and energy conservation at all levels of approximation. Both molecular and radiation field degrees of freedom are treated quantum mechanically. The formulation is based on the nonequilibrium Green's function (NEGF) approach and a double sided Feynman diagrammatic representation of the photon flux is developed. Numerical simulations are presented for a model system. Our study bridges the theoretical approaches of quantum transport and optical spectroscopy and establishes a firm basis for applying traditional tools of nonlinear optical spectroscopy in molecular optoelectronics.

cond-mat.mes-hall↗
arXiv2019

Stimulated X-ray Raman and Absorption Spectroscopy of Iron-Sulfur Dimers

Iron-sulfur complexes play an important role in biological processes such as metabolic electron transport. A detailed understanding of the mechanism of long range electron transfer requires knowledge of the electronic structure of the complexes, which has traditionally been challenging to obtain, either by theory or by experiment, but the situation has begun to change with advances in quantum chemical methods and intense free electron laser light sources. We compute the signals from stimulated X-ray Raman spectroscopy (SXRS) and absorption spectroscopy of homovalent and mixed-valence [2Fe-2S] complexes, using the {\it ab initio} density matrix renormalization group (DMRG) algorithm. The simulated spectra show clear signatures of the theoretically predicted dense low-lying excited states within the d-d manifold. Furthermore, the difference in signal intensity between the absorption-active and Raman-active states provides a potential mechanism to selectively excite states by a proper tuning of the excitation pump, to access the electronic dynamics within this manifold.

physics.chem-ph↗
arXiv2019

Quantum phase-sensitive diffraction and imaging using entangled photons

We propose a novel quantum diffraction imaging technique whereby one photon of an entangled pair is diffracted off a sample and detected in coincidence with its twin. The image is obtained by scanning the photon that did not interact with matter. We show that when a dynamical quantum system interacts with an external field, the phase information is imprinted in the state of the field in a detectable way. The contribution to the signal from photons that interact with the sample scales as $\propto I_{p}^{1/2}$, where $I_{p}$ is the source intensity, compared to $\propto I_{p}$ of classical diffraction. This makes imaging with weak-field possible, avoiding damage to delicate samples. A Schmidt decomposition of the state of the field can be used for image enhancement by reweighting the Schmidt modes contributions.

quant-ph↗
arXiv2019

Monitoring Spontaneous Charge-density Fluctuations by Single-molecule Diffraction of Quantum Light

Homodyne X-ray diffraction signals produced by classical light and classical detectors are given by the modulus square of the charge density in momentum space $\left|σ(\mathbf{q})\right|^{2}$, missing its phase which is required in order to invert the signal to real space. We show that quantum detection of the radiation field yields a linear diffraction pattern that reveals $σ(\mathbf{q})$ itself, including the phase. We further show that repeated diffraction measurements with variable delays constitute a novel multidimensional measure of spontaneous charge-density fluctuations. Classical diffraction, in contrast, only reveals a subclass of even-order correlation functions. Simulations of two dimensional signals obtained by two diffraction events are presented for the amino acid cysteine.

physics.chem-ph↗
arXiv2018

Local fluctuations of vibrational polaritons monitored by two-dimensional infrared spectroscopy

We study the collective behavior of molecules placed in an infrared (IR) microcavity, incorporating the local fluctuations, i.e., dynamical disorder. The cooperative feature in vibrational polaritons is shown to be dynamically eroded, due to intermolecule coherence. To further resolve such process, we develop a two-dimensional infrared spectroscopy (2D-IR) for molecules interacting with cavity modes. The cooperative feature in correspondence to the spectroscopic signal is specified. The results reveal the dark states by the cross peaks apart from the ones for polaritons, as a result of the breakdown of cooperativity between molecules. We further show that the breakdown of cooperativity profoundly connects to the localization of the vibrational excitations whereas the polariton modes are extended wave over several molecules. Besides, our work offers new physical insight for understanding the recent 2D-IR experiments where the interaction between dark modes and bright polaritons was evident.

quant-ph↗
arXiv2018

X-Ray sum frequency generation; direct imaging of ultrafast electron dynamics

X-ray diffraction from molecules in the ground state produces an image of their charge density, and time-resolved X-ray diffraction can thus monitor the motion of the nuclei. However, the density change of excited valence electrons upon optical excitation can barely be monitored with regular diffraction techniques due to the overwhelming background contribution of the core electrons. We present a nonlinear X-ray technique made possible by novel free electron laser sources, which provides a spatial electron density image of valence electron excitations. The technique, sum frequency generation carried out with a visible pump and a broadband X-ray diffraction pulse, yields snapshots of the transition charge densities, which represent the electron density variations upon optical excitation. The technique is illustrated by ab initio simulations of transition charge density imaging for the optically induced electronic dynamics in a donor/acceptor substituted stilbene.

physics.chem-ph↗