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Shaul Mukamel

Publications and source records attributed to Shaul Mukamel.

At least 55 records · Page 3Linked to original sources
arXiv2017

Linear and Nonlinear Time- and Frequency-Domain Spectroscopy with Multiple Frequency Combs

Two techniques that employ equally spaced trains of optical pulses to map an optical high frequency into a low frequency modulation of the signal that can be detected in real time are compared. The development of phase-stable optical frequency combs has opened up new avenues to metrology and spectroscopy. The ability to generate a series of frequency spikes with precisely controlled separation permits a fast, highly accurate sampling of the material response. Recently, pairs of frequency combs with slightly different repetition rates have been utilized to down-convert material susceptibilities from the optical to microwave regime where they can be recorded in real time. We show how this one-dimensional dual comb technique can be extended to multiple dimensions by using several combs. We demonstrate how nonlinear susceptibilities can be quickly acquired using this technique. In a second class of techniques, sequences of ultrafast mode locked laser pulses are used to recover pathways of interactions contributing to nonlinear susceptibilities by using a photo-acoustic modulation varying along the sequences. We show that these techniques can be viewed as a time-domain analogue of the multiple frequency comb scheme. %We compare the two techniques: in both, an optical high frequency is mapped into a low frequency modulation of the signal that can be detected in real time.

quant-ph↗
arXiv2017

Utilizing Microcavities to Suppress Third-order Cascades in Fifth-order Raman Spectra

Nonlinear optical signals in the condensed phase are often accompanied by sequences of lower-order processes, known as cascades, which share the same phase matching and power dependence on the incoming fields and are thus hard to distinguish. The suppression of cascading in order to reveal the desired nonlinear signal has been a major challenge in multidimensional Raman spectroscopy, i.e., the $χ^{(5)}$ signal being masked by cascading signals given by a product of two $χ^{(3)}$ processes. Since cascading originates from the exchange of a virtual photon between molecules, it can be manipulated by performing the experiment in an optical microcavity. Using a quantum electrodynamical (QED) treatment we demonstrate that the $χ^{(3)}$ cascading contributions can be greatly suppressed. By optimizing the cavity size and the incoming pulse directions, we show that up to $\sim$99.5\% suppression of the cascading signal is possible.

quant-ph↗
arXiv2017

Monitoring Nonadiabatic Avoided Crossing Dynamics in Molecules by Ultrafast X-Ray Diffraction

We examine time-resolved X-ray diffraction from molecules in the gas phase which undergo nonadiabatic avoided-crossing dynamics involving strongly coupled electrons and nuclei. Several contributions to the signal are identified, representing (in decreasing strength) elastic scattering, contributions of the electronic coherences created by nonadiabatic couplings in the avoided crossing regime, and inelastic scattering. The former probes the charge density and delivers direct information on the evolving molecular geometry. The latter two contributions are weaker and carry spatial information of the transition charge densities (off-diagonal elements of the charge-density operator). Simulations are presented for the nonadiabatic harpooning process in the excited states of sodium fluoride.

physics.chem-ph↗
arXiv2017

Discriminating Cascading Processes in Nonlinear Optics; A QED Analysis Based on Their Molecular and Geometric Origin

The nonlinear optical response of a system of molecules often contains contributions whereby the products of lower-order processes in two separate molecules give signals that appear on top of a genuine direct higher-order process with a single molecule. These many-body contributions are known as cascading and complicate the interpretation of multidimensional stimulated Raman and other nonlinear signals. In a quantum electrodynamic (QED) treatment, these cascading processes arise from second-order expansion in the molecular coupling to vacuum modes of the radiation field, i.e., single-photon exchange between molecules, which also gives rise to other collective effects. We predict the relative phase of the direct and cascading nonlinear signals and its dependence on the microscopic dynamics as well as the sample geometry. This phase may be used to identify experimental conditions for distinguishing the direct and cascading signals by their phase. Higher-order cascading processes involving the exchange of several photons between more than two molecules are discussed as well.

quant-ph↗
arXiv2016

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

Recently developed circularly polarized X-ray light sources can probe ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. We present simulations of time-resolved circular dichroism (TRCD) signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N and O) provide different local windows onto the parity breaking geometry change thus revealing enantiomer asymmetry.

physics.chem-ph↗
arXiv2016

Heterodyne-Detected Ultrafast X-Ray Diffraction and Scattering from Nonstationary States

Free-electron laser hard X-ray light sources can provide high fluence, femtosecond pulses, enabling the time-resolved probing of structural dynamics and elementary relaxation processes in molecules. Traditional X-ray elastic scattering from crystals in the ground state consists of sharp Bragg diffraction peaks that arise from pairs of molecules and reveal the ground state charge density. Scattering of ultrashort X-ray pulses from gases, liquids, and even single molecules is more complex and involves both single- and two- molecule contributions, diffuse (non-Bragg) features, elastic and inelastic components, contributions of electronic coherences in nonstationary states, and interferences between scattering off different states (heterodyne detection). We present a unified description that covers all these processes and discuss their relative magnitudes for gas-phase NaI. Conditions for the observation of holographic (heterodyne) interference, which has been recently discussed [1], are clarified.

physics.chem-ph↗
arXiv2016

Monitoring Nonadiabatic Electron-Nuclear Dynamics in Molecules by Attosecond Streaking of Photoelectrons

Streaking of photoelectrons has long been used for the temporal characterization of attosecond extreme ultraviolet pulses. When the time-resolved photoelectrons originate from a coherent superposition of electronic states, they carry an additional phase information, which can be retrieved by the streaking technique. In this contribution we extend the streaking formalism to include coupled electron and nuclear dynamics in molecules as well as initial coherences and demonstrate how it offers a novel tool to monitor non-adiabatic dynamics as it occurs in the vicinity of conical intersections and avoided crossings. Streaking can enhance the time resolution and provide direct signatures of electronic coherences, which affect many primary photochemical and biological events.

physics.chem-ph↗
arXiv2016

Giant photon gain in large-scale quantum dot circuit-QED systems

Motivated by recent experiments on the generation of coherent light in engineered hybrid quantum systems, we investigate gain in a microwave photonic cavity coupled to quantum dot structures, and develop concrete directions for achieving a giant amplification in photon transmission. We propose two architectures for scaling up the electronic gain medium: (i) $N$ double quantum dot systems (N-DQD), (ii) $M$ quantum dots arranged in series akin to a quantum cascade laser setup. In both setups, the fermionic reservoirs are voltage biased, and the quantum dots are coupled to a single-mode cavity. Optical amplification is explained based on a sum rule for the transmission function, and it is determined by an intricate competition between two different processes: charge density response in the gain medium, and cavity losses to input and output ports. The same design principle is also responsible for the corresponding giant amplification in other photonic observables, mean photon number and emission spectrum, thereby realizing a quantum device that behaves as a giant microwave amplifier.

quant-ph↗
arXiv2016

Time-and-frequency gated photon coincidence counting; a novel multidimensional spectroscopy tool

Coherent multidimensional optical spectroscopy techniques are broadly applied across the electromagnetic spectrum ranging from NMR to the UV. These reveal properties of matter through correlation plots of signal fields generated in response to sequences of short pulses with variable delays. Here we discuss a new class of multidimensional techniques obtained by time-and-frequency resolved photon coincidence counting measurements of N photons which constitutes a 2N dimensional spectrum. A compact description of these signals is developed based on time ordered superoperators rather than the normally ordered ordinary operators used in Glauber's photon counting formalism.The independent control of the time and frequency gate parameters reveals details of matter dynamics not available otherwise. Application to an anharmonic oscillator model with fluctuating energy and anharmonicity demonstrates the power of these signals.

quant-ph↗
arXiv2016

Nonlinear optical signals and spectroscopy with quantum light

Conventional nonlinear 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. We present an intuitive diagrammatic approach for calculating ultrafast spectroscopy signals induced by quantum light, focusing on applications involving entangled photons with nonclassical bandwidth properties - known as "time-energy entanglement". Nonlinear optical signals induced by quantized light fields are expressed using time ordered multipoint correlation functions of superoperators. These are different from Glauber's g- functions for photon counting which use normally ordered products of ordinary operators. Entangled photon pairs are not subjected to the classical Fourier limitations on the joint temporal and spectral resolution. After a brief survey of properties of entangled photon pairs relevant to their spectroscopic applications, different optical signals, and photon counting setups are discussed and illustrated for simple multi-level model systems.

quant-ph↗
arXiv2016

Two-dimensional Infrared Spectroscopy of vibrational polaritons of molecules in an optical cavity

Strong coupling of molecular vibrations to an infrared cavity mode affects their nature by creating dressed polariton states. We show how the single and double vibrational polariton manifolds may be controlled by varying the cavity coupling strength, and probed by a time domain 2DIR technique, Double Quantum Coherence (DQC). Applications are made to the amide-I ($CO$) and amide-II ($CN$) bond vibrations of $N-methylacetamide$ (NMA).

quant-ph↗
arXiv2016

Wigner-Lindblad equations for quantum friction

Dissipative forces are ubiquitous and thus constitute an essential part of realistic physical theories. However, quantization of dissipation has remained an open challenge for nearly a century. We construct a quantum counterpart of classical friction, a velocity-dependent force acting against the direction of motion. In particular, a translationary invariant Lindblad equation is derived satisfying the appropriate dynamical relations for the coordinate and momentum (i.e., the Ehrenfest equations). Numerical simulations establish that the model approximately equilibrates. These findings significantly advance a long search for a universally valid Lindblad model of quantum friction and open opportunities for exploring novel dissipation phenomena.

quant-ph↗
arXiv2016

Tunable photonic cavity coupled to a voltage-biased double quantum dot system: Diagrammatic NEGF approach

We investigate gain in microwave photonic cavities coupled to voltage-biased double quantum dot systems with an arbitrary strong dot-lead coupling and with a Holstein-like light-matter interaction, by adapting the diagrammatic Keldysh nonequilibrium Green's function approach. We compute out-of-equilibrium properties of the cavity : its transmission, phase response, mean photon number, power spectrum, and spectral function. We show that by the careful engineering of these hybrid light-matter systems, one can achieve a significant amplification of the optical signal with the voltage-biased electronic system serving as a gain medium. We also study the steady state current across the device, identifying elastic and inelastic tunnelling processes which involve the cavity mode. Our results show how recent advances in quantum electronics can be exploited to build hybrid light-matter systems that behave as single-atom amplifiers and photon source devices. The diagrammatic Keldysh approach is primarily discussed for a cavity-coupled double quantum dot architecture, but it is generalizable to other hybrid light-matter systems.

cond-mat.mes-hall↗
arXiv2016

Non-adiabatic dynamics of molecules in optical cavities

Strong coupling of molecules to the vacuum field of micro cavities can modify the potential energy surfaces opening new photophysical and photochemical reaction pathways. While the influence of laser fields is usually described in terms of classical field, coupling to the vacuum state of a cavity has to be described in terms of dressed photon-matter states (polaritons) which require quantized fields. We present a derivation of the non-adiabatic couplings for single molecules in the strong coupling regime suitable for the calculation of the dressed state dynamics. The formalism allows to use quantities readily accessible from quantum chemistry codes like the adiabatic potential energy surfaces and dipole moments to carry out wave packet simulations in the dressed basis. The implications for photochemistry are demonstrated for a set of model systems representing typical situations found in molecules.

quant-ph↗
arXiv2015

Catching Conical Intersections in the Act; Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals

Conical intersections (CoIn) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CoIns have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates and some vibrational signatures. We show that short X-ray (rather than optical) pulses can directly detect the passage through a CoIn with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond/attosecond X-ray pulse to detect the electronic coherences (rather than populations) that are generated as the system passes through the CoIn.

physics.chem-ph↗
arXiv2015

Non-linear non-local molecular electrodynamics with nano-optical fields

The interaction of optical fields sculpted on the nano-scale with matter may not be described by the dipole approximation since the fields vary appreciably across the molecular length scale. Rather than incrementally adding higher multipoles it is advantageous and more physically transparent to describe the optical process using non-local response functions that intrinsically include all multipoles. We present a semi-classical approach to the non-linear response functions based on the minimal coupling Hamiltonian. The first, second and third order non-local response functions are expressed in terms of correlation functions of the charge and the current densities. This approach is based on the gauge invariant current rather than the polarization, and on the vector potential rather than the electric and magnetic fields.

quant-ph↗
arXiv2015

Nonlinear fluctuations and dissipation in matter revealed by quantum light

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.

quant-ph↗