Sub-two-cycle gigawatt-peak-power LWIR OPA for ultrafast nonlinear spectroscopy of condensed state materials.

The application of high-power, few-cycle, long-wave infrared (LWIR, 8-20 µm) pulses in strong-field physics is largely unexplored due to the lack of suitable sources. However, the generation of intense pulses with >6 µm wavelength range is becoming increasingly feasible with the recent advances in high-power ultrashort lasers in the middle-infrared range that can serve as a pump for optical parametric amplifiers (OPA). Here we experimentally demonstrate the feasibility of this approach by building an OPA pumped at 2.4 µm that generates 93 µJ pulses at 9.5 µm, 1 kHz repetition rate with sub-two-cycle pulse duration, 1.6 GW peak power, and excellent beam quality. The results open a wide range of applications in attosecond physics (especially for studies of condensed phase samples), remote sensing, and biophotonics.

High-order harmonic generation from a thin film crystal perturbed by a quasi-static terahertz field.

Studies of laser-driven strong field processes subjected to a (quasi-)static field have been mainly confined to theory. Here we provide an experimental realization by introducing a bichromatic approach for high harmonic generation (HHG) in a dielectric that combines an intense 70 femtosecond duration mid-infrared driving field with a weak 2 picosecond period terahertz (THz) dressing field. We address the physics underlying the THz field induced static symmetry breaking and its consequences on the efficient production/suppression of even-/odd-order harmonics, and demonstrate the ability to probe the HHG dynamics via the modulation of the harmonic distribution. Moreover, we report a delay-dependent even-order harmonic frequency shift that is proportional to the time derivative of the THz field. This suggests a limitation of the static symmetry breaking interpretation and implies that the resultant attosecond bursts are aperiodic, thus providing a frequency domain probe of attosecond transients while opening opportunities in precise attosecond pulse shaping.

Attochemistry Regulation of Charge Migration.

Charge migration (CM) is a coherent attosecond process that involves the movement of localized holes across a molecule. To determine the relationship between a molecule's structure and the CM dynamics it exhibits, we perform systematic studies of para-functionalized bromobenzene molecules (X-C6H4-R) using real-time time-dependent density functional theory. We initiate valence-electron dynamics by emulating rapid strong-field ionization leading to a localized hole on the bromine atom. The resulting CM, which takes on the order of 1 fs, occurs via an X localized → C6H4 delocalized → R localized mechanism. Interestingly, the hole contrast on the acceptor functional group increases with increasing electron-donating strength. This trend is well-described by the Hammett σ value of the group, which is a commonly used metric for quantifying the effect of functionalization on the chemical reactivity of benzene derivatives. These results suggest that simple attochemistry principles and a density-based picture can be used to predict and understand CM.

Unveiling the Inhomogeneous Nature of Strong Field Ionization in Extended Systems.

Intense light-induced fragmentation of spherical clusters produces highly energetic ions with characteristic spatial distributions. By subjecting argon clusters to a wavelength tunable laser, we show that ion emission energy and anisotropy can be controlled through the wavelength-isotropic and energetic for shorter wavelengths and increasingly anisotropic at longer wavelengths. The anisotropic part of the energy spectrum, consisting of multiply charged high-energy ions, is considerably more prominent at longer wavelengths. Classical molecular dynamics simulations reveal that cluster ionization occurs inhomogeneously producing a columnlike charge distribution along the laser polarization direction. This previously unknown distribution results from the dipole response of the neutral cluster which creates an enhanced field at the surface, preferentially triggering ionization at the poles. The subsequently formed nanoplasma provides an additional wavelength-dependent ionization mechanism through collisional ionization, efficiently homogenizing the system only at short wavelengths close to resonance. Our results open the door to studying polarization induced effects in nanostructures and complex molecules and provide a missing piece in our understanding of anisotropic ion emission.

Investigation of Interferences in Carbon Dioxide through Multidimensional Molecular-Frame High-Harmonic Spectroscopy.

We present molecular-frame high-harmonic spectroscopic measurements of the spectral intensity and group delay of carbon dioxide. Using four different driving wavelengths and a range of intensities at each wavelength for high-harmonic generation, we observe a well-characterized minimum in the harmonic emission that exhibits both a wavelength and intensity dependence. Using the intensity dependence at each driving wavelength, we classify the minimum as due to either a structural two-center interference or dynamic multichannel interference, consistent with previous literature. By additionally measuring the group delay at each driving wavelength and intensity, we find that the sign of the group delay excursion across the interference is an acute probe of the interference mechanism. The experimental results are confirmed by ab initio time-dependent density functional theory calculations of both the spectral intensity and the phase of the harmonic emission.

Attosecond coherent electron motion in Auger-Meitner decay.

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.

Two-dimensional retrieval methods for ultrafast imaging of molecular structure using laser-induced electron diffraction.

Molecular structural retrieval based on electron diffraction has been proposed to determine the atomic positions of molecules with sub-angstrom spatial and femtosecond temporal resolutions. Given its success on small molecular systems, in this work, we point out that the accuracy of structure retrieval is constrained by the availability of a wide range of experimental data in the momentum space in all molecular systems. To mitigate the limitations, for laser-induced electron diffraction, here we retrieve molecular structures using two-dimensional (energy and angle) electron momentum spectra in the laboratory frame for a number of small molecular systems, which have previously been studied with 1D methods. Compared to the conventional single-energy or single-angle analysis, our 2D methods effectively expand the momentum range of the measured data. Besides utilization of the 2D data, two complementary methods are developed for consistency check on the retrieved results. The 2D nature of our methods also offers a way of estimating the error from retrieval, which has never been explored before. Comparing with results from prior experiments, our findings show evidence that our 2D methods outperform the conventional 1D methods. Paving the way to the retrieval of large molecular systems, in which their tunneling ionization rates are challenging to obtain, we estimate the error of using the isotropic model in place of including the orientation-dependent ionization rate.

Molecular Modes of Attosecond Charge Migration.

First-principles calculations are employed to elucidate the modes of attosecond charge migration (CM) in halogenated hydrocarbon chains. We use constrained density functional theory (DFT) to emulate the creation of a localized hole on the halogen and follow the subsequent dynamics via time-dependent DFT. We find low-frequency CM modes (∼1 eV) that propagate across the molecule and study their dependence on length, bond order, and halogenation. We observe that the CM speed (∼4 Å/fs) is largely independent of molecule length, but is lower for triple-bonded versus double-bonded molecules. Additionally, as the halogen mass increases, the hole travels in a more particlelike manner as it moves across the molecule. These heuristics will be useful in identifying molecules and optimal CM detection methods for future experiments, especially for halogenated hydrocarbons which are promising targets for ionization-triggered CM.

Universal High-Energy Photoelectron Emission from Nanoclusters Beyond the Atomic Limit.

Rescattering by electrons on classical trajectories is central to understand photoelectron and high-harmonic emission from isolated atoms or molecules in intense laser pulses. By controlling the cluster size and the quiver amplitude of electrons, we demonstrate how rescattering influences the energy distribution of photoelectrons emitted from noble gas nanoclusters. Our experiments reveal a universal dependence of photoelectron energy distributions on the cluster size when scaled by the field driven electron excursion, establishing a unified rescattering picture for extended systems with the known atomic dynamics as the limit of zero extension. The result is supported by molecular dynamics calculations and rationalized with a one-dimensional classical model.

Attosecond transient absorption spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy.

The recent demonstration of isolated attosecond pulses from an X-ray free-electron laser (XFEL) opens the possibility for probing ultrafast electron dynamics at X-ray wavelengths. An established experimental method for probing ultrafast dynamics is X-ray transient absorption spectroscopy, where the X-ray absorption spectrum is measured by scanning the central photon energy and recording the resultant photoproducts. The spectral bandwidth inherent to attosecond pulses is wide compared to the resonant features typically probed, which generally precludes the application of this technique in the attosecond regime. In this paper we propose and demonstrate a new technique to conduct transient absorption spectroscopy with broad bandwidth attosecond pulses with the aid of ghost imaging, recovering sub-bandwidth resolution in photoproduct-based absorption measurements.

High relative-phase precision beam duplicator for mid-infrared femtosecond pulses.

In this Letter, we use a 0-π square-wave phase grating to shape 1350 nm and 1450 nm femtosecond pulses and create two intense lobes at the focus of a lens. We show that the relative phase between these two lobes (the 1st and -1st orders of diffraction of the grating) is controlled very simply and precisely by shifting the position of the grating in its plane. We generate high harmonic orders from the two bright lobes and record the beating between the two emissions for each harmonic order up to the 53rd harmonic order.

Disentangling Spectral Phases of Interfering Autoionizing States from Attosecond Interferometric Measurements.

We have determined spectral phases of Ne autoionizing states from extreme ultraviolet and midinfrared attosecond interferometric measurements and ab initio full-electron time-dependent theoretical calculations in an energy interval where several of these states are coherently populated. The retrieved phases exhibit a complex behavior as a function of photon energy, which is the consequence of the interference between paths involving various resonances. In spite of this complexity, we show that phases for individual resonances can still be obtained from experiment by using an extension of the Fano model of atomic resonances. As simultaneous excitation of several resonances is a common scenario in many-electron systems, the present work paves the way to reconstruct electron wave packets coherently generated by attosecond pulses in systems larger than helium.

High-harmonic spectroscopy of transient two-center interference calculated with time-dependent density-functional theory.

We demonstrate high-harmonic spectroscopy in many-electron molecules using time-dependent density-functional theory. We show that a weak attosecond-pulse-train ionization seed that is properly synchronized with the strong driving mid-infrared laser field can produce experimentally relevant high-harmonic generation (HHG) signals, from which we extract both the spectral amplitude and the target-specific phase (group delay). We also show that further processing of the HHG signal can be used to achieve molecular-frame resolution, i.e., to resolve the contributions from rescattering on different sides of an oriented molecule. In this framework, we investigate transient two-center interference in CO2 and OCS, and how subcycle polarization effects shape the oriented/aligned angle-resolved spectra.

Diffractive Imaging of C_{60} Structural Deformations Induced by Intense Femtosecond Midinfrared Laser Fields.

Theoretical studies indicated that C_{60} exposed to linearly polarized intense infrared pulses undergoes periodic cage structural distortions with typical periods around 100 fs (1 fs=10^{-15} s). Here, we use the laser-driven self-imaging electron diffraction technique, previously developed for atoms and small molecules, to measure laser-induced deformation of C_{60} in an intense 3.6 µm laser field. A prolate molecular elongation along the laser polarization axis is determined to be (6.1±1.4)% via both angular- and energy-resolved measurements of electrons that are released, driven back, and diffracted from the molecule within the same laser field. The observed deformation is confirmed by density functional theory simulations of nuclear dynamics on time-dependent adiabatic states and indicates a nonadiabatic excitation of the h_{g}(1) prolate-oblate mode. The results demonstrate the applicability of laser-driven electron diffraction methods for studying macromolecular structural dynamics in four dimensions with atomic time and spatial resolutions.

The roles of photo-carrier doping and driving wavelength in high harmonic generation from a semiconductor.

High-harmonic generation from gases produces attosecond bursts and enables high-harmonic spectroscopy to explore electron dynamics in atoms and molecules. Recently, high-harmonic generation from solids has been reported, resulting in novel phenomena and unique control of the emission, absent in gas-phase media. Here we investigate high harmonics from semiconductors with controllable induced photo-carrier densities, as well as the driving wavelengths. We demonstrate that the dominant generation mechanism can be identified by monitoring the variation of the harmonic spectra with the carrier density. Moreover, the harmonic spectral dependence on the driving wavelength is reported and a different dependence from the well-known one in gas-phase media is observed. Our study provides distinct control of the harmonic process from semiconductors, sheds light on the underlying mechanism and helps optimize the harmonic properties for future solid-state attosecond light sources.

Tunable mid-infrared source of light carrying orbital angular momentum in the femtosecond regime.

We report on a tunable intense femtosecond mid-infrared (mid-IR) light source carrying orbital angular momentum (OAM). Our setup is based on an optical parametric amplification system with an 800 nm pump shaped with a spiral phase plate. We confirm the anisotropic OAM transfer from the pump to the idler through stimulated difference frequency generation by measuring the diffraction patterns of a triangular aperture illuminated by the signal, pump, and idler beams. The tunability of the setup is demonstrated by performing measurements at 3.0 and 3.6 µm idler wavelengths. This result provides a robust method of controlling OAM in strong field physics and designing secondary sources carrying OAM in the extreme ultraviolet spectral range through high-order harmonics generation.

High-order harmonic generations in intense MIR fields by cascade three-wave mixing in a fractal-poled LiNbO3 photonic crystal.

We report on the generation of harmonic-like photon upconversion in a LiNbO3-based nonlinear photonic crystal by mid-infrared (MIR) femtosecond laser pulses. We study below bandgap harmonics of various driver wavelengths, reaching up to the 11th order at 4 µm driver with 13% efficiency. We compare our results to numerical simulations based on two mechanisms: cascade three-wave mixing and non-perturbative harmonic generation, both of which include quasi-phase matching. The cascade model reproduces well the general features of the observed spectrum, including a plateau-like harmonic distribution and the observed efficiency. This has the potential for providing a source of tabletop few femtosecond ultraviolet pulses.

High-energy mid-infrared sub-cycle pulse synthesis from a parametric amplifier.

High-energy phase-stable sub-cycle mid-infrared pulses can provide unique opportunities to explore phase-sensitive strong-field light-matter interactions in atoms, molecules and solids. At the mid-infrared wavelength, the Keldysh parameter could be much smaller than unity even at relatively modest laser intensities, enabling the study of the strong-field sub-cycle electron dynamics in solids without damage. Here we report a high-energy sub-cycle pulse synthesiser based on a mid-infrared optical parametric amplifier and its application to high-harmonic generation in solids. The signal and idler combined spectrum spans from 2.5 to 9.0 µm. We coherently synthesise the passively carrier-envelope phase-stable signal and idler pulses to generate 33 µJ, 0.88-cycle, multi-gigawatt pulses centred at ~4.2 µm, which is further energy scalable. The mid-infrared sub-cycle pulse is used for driving high-harmonic generation in thin silicon samples, producing harmonics up to ~19th order with a continuous spectral coverage due to the isolated emission by the sub-cycle driver.Stable sub-cycle pulses in the mid-infrared region allow damage-free investigation of electron dynamics in solids. Here, the authors develop a suitable source to this end which is based on an optical parametric amplifier.

Laser induced periodic surface structure formation in germanium by strong field mid IR laser solid interaction at oblique incidence.

Laser induced periodic surface structures (LIPSS or ripples) were generated on single crystal germanium after irradiation with multiple 3 µm femtosecond laser pulses at a 45° angle of incidence. High and low spatial frequency LIPSS (HSFL and LSFL, respectively) were observed for both s- and p-polarized light. The measured LSFL period for p-polarized light was consistent with the currently established LIPSS origination model of coupling between surface plasmon polaritons (SPP) and the incident laser pulses. A vector model of SPP coupling is introduced to explain the formation of s-polarized LSFL away from the center of the damage spot. Additionally, a new method is proposed to determine the SPP propagation length from the decay in ripple depth. This is used along with the measured LSFL period to estimate the average electron density and Drude collision time of the laser-excited surface. Finally, full-wave electromagnetic simulations are used to corroborate these results while simultaneously offering insight into the nature of LSFL formation.

Diffraction using laser-driven broadband electron wave packets.

Directly monitoring atomic motion during a molecular transformation with atomic-scale spatio-temporal resolution is a frontier of ultrafast optical science and physical chemistry. Here we provide the foundation for a new imaging method, fixed-angle broadband laser-induced electron scattering, based on structural retrieval by direct one-dimensional Fourier transform of a photoelectron energy distribution observed along the polarization direction of an intense ultrafast light pulse. The approach exploits the scattering of a broadband wave packet created by strong-field tunnel ionization to self-interrogate the molecular structure with picometre spatial resolution and bond specificity. With its inherent femtosecond resolution, combining our technique with molecular alignment can, in principle, provide the basis for time-resolved tomography for multi-dimensional transient structural determination.