Over the past decade, ultrafast electron dynamics in the solid state have been extensively studied using various strong light-matter interaction techniques, such as high-harmonic generation. These studies lead to multiple interpretations of light-matter interaction in the strong-field regime, with exact mechanisms not yet fully understood. It is well known that strong-field interaction with a crystalline solid leads to substantial modification of its band structure and, hence, its optical properties on ultrafast timescales. In this work, we present measurements of ultrafast electric-field observables in magnesium oxide using a nonresonant nonlinear optical interaction. Using field observables, we show that strong laser fields modulate the band structure on subcycle timescales, thereby altering the material's nonlinear optical response. We perform time-dependent perturbation theory calculations using a field-dependent dispersion relation and semiconductor Bloch equation calculations, both of which agree with experimental observations. Furthermore, we extract pulse decay times from the real-time signal electric field envelope and show subcycle control of dephasing times. Our work offers a new perspective on strong field-driven electron dynamics in solids through electric-field observables. The demonstrated attosecond modulation of the nonlinear response could have important implications for quantum light generation and quantum spectroscopy using nonlinear optical processes.

We propose a broadband, femtosecond two-photon excitation scheme for efficient population transfer to the ultranarrow linewidth 1s2s^{1}S_{0} metastable state in helium. Using 120 nm vacuum ultraviolet femtosecond laser pulses, we theoretically demonstrate that a direct two-photon excitation process can achieve a population transfer efficiency of 25%–30%, even when photoionization losses are included. The use of broadband pulses enables multiple excitation pathways to populate the excited state, in addition to compensating for significant ac Stark shifts occurring within the pulse duration. Furthermore, we introduce a two-color two-photon extreme-ultraviolet-near-infrared (XUV-IR) excitation scheme that will further reduce ionization losses and can achieve significantly higher transfer efficiencies of ∼70%. These results demonstrate that high excitation probability of ultranarrow linewidth (∼50Hz) excited states can be achieved using experimentally accessible femtosecond laser sources with bandwidth in the terahertz range.

We present an experimental and theoretical study of the interplay between ultrafast electron dynamics and librational dynamics in liquid nitrobenzene. A femtosecond ultraviolet pulse and two femtosecond near-infrared pulses interact with nitrobenzene molecules, generating a four-wave mixing nonlinear signal measured in the Optical Kerr Effect geometry. The signal is measured to be nonzero only at negative time delays, corresponding to the near-infrared pulses arriving before the ultraviolet pulse. We perform time-dependent Quantum Master Equation calculations with classical libration to simulate the experiment. The simulations support the conclusion that the near-infrared pulses launch librational motion while creating electronic coherences resulting in a libration-modulated electronic nonlinear response. The analysis of the phase-matched four-wave mixing signals suggests a nonparametric process leaving the molecules in an excited electronic state, providing new insight into ultrafast nonlinear optical interactions in liquids and advancing toward probing ultrafast electronic coherences in complex molecular liquids.

Squeezed light is a key resource in quantum metrology and quantum information science. It is primarily generated through nonlinear optical interactions, where the degree of squeezing is set by the nonlinearity of the medium. Here, we modulate the third-order nonlinear response of a dielectric with strong ultrafast laser fields to control squeezed light generation on attosecond time scales. By tuning a sub-cycle phase delay between the input femtosecond pulses, we switch the generated light between amplitude-squeezed and phase-squeezed states. We measure the quantum noise using a frequency-resolved balanced homodyne detection scheme that extracts field quadratures in many frequency modes simultaneously. From these measurements we obtain the complete coherency matrix containing quadrature correlations across the frequency modes of the pulse. These results enable quantum light sources with sub-cycle control of squeezing and open a route to transduction of dynamical quantum correlations in matter to quantum correlations in electric fields.

In ultrafast time-resolved experiments with gas phase molecules, the alignment of the molecular axis relative to the polarization of the interacting laser pulses plays a crucial role in determining the dynamics following this light-matter interaction. The molecular axis distribution is influenced by the interacting pulses and is intrinsically linked to the electronic coherences of the excited molecules. However, in typical theoretical calculations of such interactions, the signal is either calculated for a single molecule in the molecular frame or averaged over all possible molecular orientations to compare with the experiment. Such averaging removes information about anisotropy in the molecular-axis distribution, even though anisotropic contributions can play a significant role in the measured experimental signal. Here, we calculate the laboratory frame transient electronic first-order polarization [P(1)] spectra in terms of separated molecular frame and laboratory frame quantities. The laboratory frame polarizations are compared with orientation-averaged quantum master equation calculations, demonstrating that orientation-averaging captures only the isotropic contributions. We show that our formalism also allows us to evaluate the anisotropic contributions to the spectrum. Finally, we discuss the application of this approach to achieve ultrafast quantum state tomography using transient absorption spectroscopy and field observables in nonlinear spectroscopy.

The name of an author in the article by Walter et al. (2022) [J. Synchrotron Rad. 29, 957–968] is corrected.

We describe an experiment to measure the emitted real-time electric field from an ultrafast third-order nonlinear optical interaction in molecules, using a phase-tracked spectral interferometry scheme. By combining a software lock-in amplification based spectrometer with spectral interferometry, we measure the electric field of the nonlinear optical signal from rotationally excited gas-phase molecules. The lock-in spectrometer allows selective measurement of signals of interest with improved signal-to-noise ratio, while rejecting any unwanted incoherent background. The nonlinear optical signal interferes with a known reference pulse on the spectrometer, which allows measurement of ultraweak signal electric fields. Further, we show that lock-in detection enables correction of slow interferometric drifts by utilizing a multidimensional measurement space. Thus, interferometric stability is achieved without the need for active stabilization, which typically utilizes an independent phase drift measurement. We present data from an experiment in impulsively aligned molecules that demonstrates the important features of our scheme. The scheme can be applied to study ultrafast dynamics in laser excited systems in the gas, liquid, and solid phases of matter.

We resolve the real-time electric field of a femtosecond third-order nonlinear optical signal in the molecular frame. The electric field emitted by the induced third-order polarization from impulsively pre-aligned gas-phase molecules at room temperature, in a degenerate four-wave mixing (DFWM) scheme, is measured using a spectral interferometry technique. We show that by measuring both the amplitude and phase of the emitted femtosecond pulse, information related to electronic symmetries can be accessed. The nonlinear signal is measured around a rotational revival to extract its molecular-frame angle dependence from pump-probe time delay scans. By comparing these measurements for two linear molecules, carbon dioxide (CO2) and Nitrogen (N2), we show that the measured second-order phase parameter (temporal chirp) of the signal is sensitive to the valence electronic symmetry of the molecules, whereas the amplitude of the signal does not show such sensitivity. We compare these measurements to theoretical calculations of the chirp observable in the molecular frame. This work is an important step towards using field-resolved nonlinear optical measurements to study ultrafast dynamics in electronically excited molecules.

The photoelectric effect is not truly instantaneous, but exhibits attosecond delays that can reveal complex molecular dynamics. Sub-femtosecond duration light pulses provide the requisite tools to resolve the dynamics of photoionization. Accordingly, the past decade has produced a large volume of work on photoionization delays following single photon absorption of an extreme ultraviolet (XUV) photon. However, the measurement of time-resolved core-level photoionization remained out of reach. The required x-ray photon energies needed for core-level photoionization were not available with attosecond tabletop sources. We have now measured the x-ray photoemission delay of core-level electrons, and here report unexpectedly large delays, ranging up to 700 attoseconds in NO near the oxygen K-shell threshold. These measurements exploit attosecond soft x-ray pulses from a free-electron laser (XFEL) to scan across the entire region near the K-shell threshold. Furthermore, we find the delay spectrum is richly modulated, suggesting several contributions including transient trapping of the photoelectron due to shape resonances, collisions with the Auger-Meitner electron that is emitted in the rapid non-radiative relaxation of the molecule, and multi-electron scattering effects. The results demonstrate how x-ray attosecond experiments, supported by comprehensive theoretical modelling, can unravel the complex correlated dynamics of core-level photoionization.

We report an experiment to measure the femtosecond electric field of the signal emitted from an optical third-order nonlinear interaction in carbon dioxide molecules. Using degenerate four-wave mixing with femtosecond near infrared laser pulses in combination with the ultra-weak femtosecond pulse measurement technique of TADPOLE, we measure the nonlinear signal electric field in the time domain at different time delays between the interacting pulses. The chirp extracted from the temporal phase of the emitted nonlinear signal is found to sensitively depend on the electronic and rotational contributions to the nonlinear response. While the rotational contribution results in a nonlinear signal chirp close to the chirp of the input pulses, the electronic contribution results in a significantly higher chirp which changes with time delay. Our work demonstrates that electric field-resolved nonlinear spectroscopy offers detailed information on nonlinear interactions at ultrafast time scales.

Free-electron lasers (FEL), with their ultrashort pulses, ultrahigh intensities, and high repetition rates at short wavelength, have provided new approaches to Atomic and Molecular Optical Science. One such approach is following the birth of a photo electron to observe ion dynamics on an ultrafast timescale. Such an approach presents the opportunity to decipher the photon-initiated structural dynamics of an isolated atomic and molecular species. It is a fundamental step towards understanding single- and non-linear multi-photon processes and coherent electron dynamics in atoms and molecules, ultimately leading to coherent control following FEL research breakthroughs in pulse shaping and polarization control. A key aspect for exploring photoinduced quantum phenomena is visualizing the collective motion of electrons and nuclei in a single reaction process, as dynamics in atoms/ions proceed at femtosecond (10−15 s) timescales while electronic dynamics take place in the attosecond timescale (10−18 s). Here, we report on the design of a Dynamic Reaction Microscope (DREAM) endstation located at the second interaction point of the Time-Resolved Molecular and Optical (TMO) instrument at the Linac Coherent Light Source (LCLS) capable of following the photon–matter interactions by detecting ions and electrons in coincidence. The DREAM endstation takes advantage of the pulse properties and high repetition rate of LCLS-II to perform gas-phase soft X-ray experiments in a wide spectrum of scientific domains. With its design ability to detect multi-ions and electrons in coincidence while operating in step with the high repetition rate of LCLS-II, the DREAM endstation takes advantage of the inherent momentum conservation of reaction product ions with participating electrons to reconstruct the original X-ray photon–matter interactions. In this report, we outline in detail the design of the DREAM endstation and its functionality, with scientific opportunities enabled by this state-of-the-art instrument.

The newly constructed time-resolved atomic, molecular and optical science instrument (TMO) is configured to take full advantage of both linear accelerators at SLAC National Accelerator Laboratory, the copper accelerator operating at a repetition rate of 120 Hz providing high per-pulse energy as well as the superconducting accelerator operating at a repetition rate of about 1 MHz providing high average intensity. Both accelerators power a soft X-ray free-electron laser with the new variable-gap undulator section. With this flexible light source, TMO supports many experimental techniques not previously available at LCLS and will have two X-ray beam focus spots in line. Thereby, TMO supports atomic, molecular and optical, strong-field and nonlinear science and will also host a designated new dynamic reaction microscope with a sub-micrometer X-ray focus spot. The flexible instrument design is optimized for studying ultrafast electronic and molecular phenomena and can take full advantage of the sub-femtosecond soft X-ray pulse generation program.

In quantum systems, coherent superpositions of electronic states evolve on ultrafast time scales (few femtoseconds to attoseconds; 1 attosecond = 0.001 femtoseconds = 10 −18 seconds), leading to a time-dependent charge density. Here we performed time-resolved measurements using attosecond soft x-ray pulses produced by a free-electron laser, to track the evolution of a coherent core-hole excitation in nitric oxide. Using an additional circularly polarized infrared laser pulse, we created a clock to time-resolve the electron dynamics and demonstrated control of the coherent electron motion by tuning the photon energy of the x-ray pulse. Core-excited states offer a fundamental test bed for studying coherent electron dynamics in highly excited and strongly correlated matter.

We propose the generation of attosecond entangled bi-photons in the extreme-ultraviolet regime by two-photon decay of a metastable atomic state as a source similar to spontaneous parametric down-conversion photons. The 1s2s 1 S 0 metastable state in helium decays to the ground state by emission of two energy-time entangled photons with a photon bandwidth equal to the total energy spacing of 20.62 eV. This results in a pair correlation time in the attosecond regime making these entangled photons a highly suitable source for attosecond pump-probe experiments. The bi-photon generation rate from a direct four photon excitation of helium at 240 nm is calculated and used to assess some feasible schemes to generate these bi-photons. Possible applications of entangled bi-photons in attosecond time scale experiments, and a discussion of their potential to reach the zeptosecond regime are presented. Abstract This supplementary material provides details on the calculation of the geometry factor for the spheroid cavity, estimates for the entangled bi-photon generation rates in various schemes, and estimates for photoionization rates from entangled two-photon absorption in an attosecond pump-probe experiment.

Optically active spin defects in wide-bandgap materials have many potential applications in quantum information and quantum sensing. Spin defects in two-dimensional layered van der Waals materials are just emerging to be investigated. Here we demonstrate that optically addressable spin ensembles in hexagonal boron nitride (hBN) can be generated by femtosecond laser irradiation. We observe optically detected magnetic resonance (ODMR) of hBN spin defects created by laser irradiation. We show that the creation of spin defects in hBN is strongly affected by the pulse energy of the femtosecond laser. When the laser pulse number is less than a few thousand, the pulse number only affects the density of the defects but not the type of defects. With proper laser parameters, spin defects can be generated with a high probability of success. Our work provides a convenient way to create spin defects in hBN by femtosecond laser writing, which shows promising prospects for quantum technologies.

Clusters in 3He and 4He nanodroplets reveal markedly different shapes showcasing the effect of superfluidity on aggregation.