arXiv subjects

S. Mukamel

Publications and source records attributed to S. Mukamel.

16 recordsLinked to original sources

arXiv2024

Ultrafast photochemistry and electron-diffraction spectra in n->(3s) Rydberg excited cyclobutanone resolved at the multireference perturbative level

We study the ultrafast time evolution of cyclobutanone excited to singlet n-->Rydberg state through XMS-CASPT2 nonadiabatic surface-hopping simulations. These dynamics predict relaxation to ground-state with a timescale of 822 +/- 45 fs with minimal involvement of triplets. The major relaxation path to the ground-state involves a three-state degeneracy region and leads to variety of fragmented photoproducts. We simulate the resulting time-resolved electron-diffraction spectra which track the relaxation of the excited state and the formation of various photoproducts in the ground-state.

physics.chem-ph↗

arXiv2021

Transient measurement of phononic states with covariance-based stochastic spectroscopy

We present a novel approach to transient Raman spectroscopy, which combines stochastic probe pulses and a covariance-based detection to measure stimulated Raman signals in alpha-quartz. A coherent broadband pump is used to simultaneously impulsively excite a range of different phonon modes, and the phase, amplitude, and energy of each mode are independently recovered as a function of the pump-probe delay by a noisy-probe and covariance-based analysis. Our experimental results and the associated theoretical description demonstrate the feasibility of 2D-Raman experiments based on the stochastic probe schemes, with new capabilities not available in equivalent mean-value-based 2D-Raman techniques. This work unlocks the gate for nonlinear spectroscopies to capitalize on the information hidden within the noise and overlooked by a mean-value analysis.

physics.optics↗

arXiv2018

Femtosecond Covariance Spectroscopy

The success of non-linear optics relies largely on pulse-to-pulse consistency. In contrast, covariance based techniques used in photoionization electron spectroscopy and mass spectrometry have shown that wealth of information can be extracted from noise that is lost when averaging multiple measurements. Here, we apply covariance based detection to nonlinear optical spectroscopy, and show that noise in a femtosecond laser is not necessarily a liability to be mitigated, but can act as a unique and powerful asset. As a proof of principle we apply this approach to the process of stimulated Raman scattering in alpha-quartz. Our results demonstrate how nonlinear processes in the sample can encode correlations between the spectral components of ultrashort pulses with uncorrelated stochastic fluctuations. This in turn provides richer information compared to the standard non-linear optics techniques that are based on averages over many repetitions with well-behaved laser pulses. These proof-of-principle results suggest that covariance based nonlinear spectroscopy will improve the applicability of fs non-linear spectroscopy in wavelength ranges where stable, transform limited pulses are not available such as, for example, x-ray free electron lasers which naturally have spectrally noisy pulses ideally suited for this approach.

physics.optics↗

arXiv2014

Probing chirality fluctuations in molecules by nonlinear optical spectroscopy

Symmetry breaking caused by geometric fluctuations can enable processes that are otherwise forbidden. An example is a perylene bisimide dyad whose dipole moments are perpendicular to each other. Förster-type energy transfer is thus forbidden at the equilibrium geometry since the dipolar coupling vanishes. Yet, fluctuations of the geometric arrangement have been shown to induce finite energy transfer that depends on the dipole variance, rather than the mean. We demonstrate an analogous effect associated with chirality symmetry breaking. In its equilibrium geometry this dimer is non chiral. The linear chiral response which depends on the average geometry thus vanishes. However, we show that certain 2D chiral optical signals are finite due to geometric fluctuations. Furthermore, the correlation time of these fluctuations can be experimentally revealed by the waiting time dependence of the 2D signal.

physics.chem-ph↗

arXiv2014

Nonlinear Spectroscopy of Controllable Many-Body Quantum Systems

We establish a novel approach to probing spatially resolved multi-time correlation functions of interacting many-body systems, with scalable experimental overhead. Specifically, designing nonlinear measurement protocols for multidimensional spectra in a chain of trapped ions with single-site addressability enables us, e.g., to distinguish coherent from incoherent transport processes, to quantify potential anharmonicities, and to identify decoherence-free subspaces.

quant-ph↗

arXiv2012

Reconstruction of the wavefunctions of coupled nanoscopic emitters using a coherent optical technique

We show that using coherent, spatially resolved spectroscopy, complex hybrid wave functions can be disentangled into the individual wave functions of the individual emitters. This way, detailed information on the coupling of the individual emitters, not available in far-field spectroscopy can be obtained. The proposed quantum state tomography relies on the ability to selectively excite each emitter individually by spatially localized pulses. Simulations of coupled semiconductor Ga/InAs quantum dots, using light fields available in current nanoplasmonics, show that even undesired resonances can be removed from measured spectra. The method can also be applied to study the internal coupling of pigments in photosythesis and artificial light harvesting.

cond-mat.mes-hall↗

arXiv2011

Trapping photon-dressed Dirac electrons in a quantum dot studied by coherent two dimensional photon echo spectroscopy

We study the localization of dressed Dirac electrons in a cylindrical quantum dot (QD) formed on monolayer and bilayer graphene by spatially different potential profiles. Short lived excitonic states which are too broad to be resolved in linear spectroscopy are revealed by cross peaks in the photon-echo nonlinear technique. Signatures of the dynamic gap in the two-dimensional spectra are discussed. The effect of the Coulomb induced exciton-exciton scattering and the formation of biexciton molecules are demonstrated.

cond-mat.mtrl-sci↗

arXiv2011

The proton momentum distribution in strongly H-bonded phases of water; a critical test of electrostatic models

Water is often viewed as a collection of monomers interacting electrostatically with each other. We compare the water proton momentum distributions from recent neutron scattering data with those calculated from two electronic structure based models. We find that below 500 K the electrostatic models are not able to even qualitatively account for the sizable vibrational zero-point contribution to the enthalpy of vaporization. This discrepancy is evidence that the change in the proton well upon solvation cannot be entirely explained by electrostatic effects alone.

physics.chem-ph↗

arXiv2009

Many-body Green's function approach to attosecond nonlinear X-ray spectroscopy

Closed expressions are derived for resonant multidimensional X-ray spectroscopy using the quasiparticle nonlinear exciton representation of optical response. This formalism is applied to predict coherent four wave mixing signals which probe single and two core-hole states. Nonlinear X-ray signals are compactly expressed in terms of one- and two- particle Green's functions which can be obtained from the solution of Hedin-like equations at the $GW$ level.

cond-mat.str-el↗

arXiv2009

Nonlinear spectroscopy with entangled photons; manipulating quantum pathways of matter

Optical signals obtained by the material response to classical laser fields are given by nonlinear response functions which can be expressed by sums over various quantum pathways of matter. We show that some pathways can be selected by using nonclassical fields, through the entanglement of photon and material pathways, which results in a different-power law dependence on the incoming field intensity. Spectrally overlapping stimulated Raman scattering (SRS) and two-photon-absorption (TPA) pathways in a pump probe experiment are separated by controlling the degree of entanglement of pairs of incoming photons. Pathway-selectivity opens up new avenues for mapping photon into material entanglement. New material information, otherwise erased by interferences among pathways, is revealed.

cond-mat.mtrl-sci↗

arXiv2008

Superoperator nonequilibrium Green's function theory of many-body systems; Applications to charge transfer and transport in open junctions

Nonequilibrium Green's functions provide a powerful tool for computing the dynamical response and particle exchange statistics of coupled quantum systems. We formulate the theory in terms of the density matrix in Liouville space and introduce superoperator algebra that greatly simplifies the derivation and the physical interpretation of all quantities. Expressions for various observables are derived directly in real time in terms of superoperator nonequilibrium Green's functions (SNGF), rather than the artificial time-loop required in Schwinger's Hilbert-space formulation. Applications for computing interaction energies, charge densities, average currents, current induced fluorescence, electroluminescence and current fluctuation (electron counting) statistics are discussed.

cond-mat.mes-hall↗

arXiv2007

Probing anomalous relaxation by coherent multidimensional optical spectroscopy

We propose to study the origin of algebraic decay of two-point correlation functions observed in glasses, proteins, and quantum dots by their nonlinear response to sequences of ultrafast laser pulses. Power-law spectral singularities and temporal relaxation in two-dimensional correlation spectroscopy (2DCS) signals are predicted for a continuous time random walk model of stochastic spectral jumps in a two level system with a power-law distribution of waiting times $ψ(t)\sim t^{-α-1}$. Spectroscopic signatures of stationary ensembles for $1<α<2$ and aging effects in nonstationary ensembles with $0<α<1$ are identified.

cond-mat.soft↗

arXiv2004

Superoperator Many-body Theory of Molecular Currents: Non-equilibrium Green Functions in Real Time

The electric conductance of a molecular junction is calculated by recasting the Keldysh formalism in Liouville space. Dyson equations for nonequilibrium many body Green's functions (NEGF) are derived directly in real (physical) time. The various NEGFs appear naturally in the theory as time ordered products of superoperators, while the Keldysh forward/backward time loop is avoided.

quant-ph↗

arXiv2003

Nonlinear Response Functions of Strongly Correlated Boson Fields: Bose-Einstein Condensates and Fractional Quantum Hall Systems

The second order response functions and susceptibilities of finite temperature Bose-Einstein Condensates (BEC) in a one dimensional harmonic trap driven by an external field that couples to the particle density are calculated by solving the time-dependent Hartree-Fock-Bogoliubov (TDHFB) equations. These provide additional insight into BEC dynamics, beyond the linear response regime. The results also apply to electron liquids in the Fractional Quantum Hall Effect (FQHE) regime which can be mapped onto an effective boson system coupled to a Chern-Simons gauge field.

cond-mat.mes-hall↗

arXiv2003

Generalized coherent state representation of Bose-Einstein condensates

We show that the quantum many-body state of Bose-Einstein condensates (BEC) consistent with the time-dependent Hartree-Fock-Bogoliubov (TDHFB) equations is a generalized coherent state (GCS). At zero temerature, the non-condensate density and the anomalous non-condensate correlation are not independent, allowing us to elimiate one of the three variables in the TDHFB.

cond-mat.soft↗

arXiv2003

Mechanical response functions of finite temperature Bose-Einstein Condensates

Using the Liouville space framework developed in nonlinear optics we calculate the linear response functions and susceptibilities of Bose-Einstein condensates (BEC) subject to an arbitrary mechanical force. Distinct signatures of the dynamics of finite temperature BEC are obtained by solving the Hartree-Fock-Bogoliubov theory. Numerical simulations of the position dependent linear response functions of one dimensional trapped BEC in the time and the frequency domains are presented.

cond-mat.soft↗