Observation of Rabi dynamics with a short-wavelength free-electron laser.

Rabi oscillations are periodic modulations of populations in two-level systems interacting with a time-varying field1. They are ubiquitous in physics with applications in different areas such as photonics2, nano-electronics3, electron microscopy4 and quantum information5. While the theory developed by Rabi was intended for fermions in gyrating magnetic fields, Autler and Townes realized that it could also be used to describe coherent light-matter interactions within the rotating-wave approximation6. Although intense nanometre-wavelength light sources have been available for more than a decade7-9, Rabi dynamics at such short wavelengths has not been directly observed. Here we show that femtosecond extreme-ultraviolet pulses from a seeded free-electron laser10 can drive Rabi dynamics between the ground state and an excited state in helium atoms. The measured photoelectron signal reveals an Autler-Townes doublet and an avoided crossing, phenomena that are both fundamental to coherent atom-field interactions11. Using an analytical model derived from perturbation theory on top of the Rabi model, we find that the ultrafast build-up of the doublet structure carries the signature of a quantum interference effect between resonant and non-resonant photoionization pathways. Given the recent availability of intense attosecond12 and few-femtosecond13 extreme-ultraviolet pulses, our results unfold opportunities to carry out ultrafast manipulation of coherent processes at short wavelengths using free-electron lasers.

Attosecond pulse shaping using a seeded free-electron laser.

Attosecond pulses are central to the investigation of valence- and core-electron dynamics on their natural timescales1-3. The reproducible generation and characterization of attosecond waveforms has been demonstrated so far only through the process of high-order harmonic generation4-7. Several methods for shaping attosecond waveforms have been proposed, including the use of metallic filters8,9, multilayer mirrors10 and manipulation of the driving field11. However, none of these approaches allows the flexible manipulation of the temporal characteristics of the attosecond waveforms, and they suffer from the low conversion efficiency of the high-order harmonic generation process. Free-electron lasers, by contrast, deliver femtosecond, extreme-ultraviolet and X-ray pulses with energies ranging from tens of microjoules to a few millijoules12,13. Recent experiments have shown that they can generate subfemtosecond spikes, but with temporal characteristics that change shot-to-shot14-16. Here we report reproducible generation of high-energy (microjoule level) attosecond waveforms using a seeded free-electron laser17. We demonstrate amplitude and phase manipulation of the harmonic components of an attosecond pulse train in combination with an approach for its temporal reconstruction. The results presented here open the way to performing attosecond time-resolved experiments with free-electron lasers.

Wave packet dynamics and control in excited states of molecular nitrogen.

Wave packet interferometry with vacuum ultraviolet light has been used to probe a complex region of the electronic spectrum of molecular nitrogen, N2. Wave packets of Rydberg and valence states were excited by using double pulses of vacuum ultraviolet (VUV), free-electron-laser (FEL) light. These wave packets were composed of contributions from multiple electronic states with a moderate principal quantum number (n ∼ 4-9) and a range of vibrational and rotational quantum numbers. The phase relationship of the two FEL pulses varied in time, but as demonstrated previously, a shot-by-shot analysis allows the spectra to be sorted according to the phase between the two pulses. The wave packets were probed by angle-resolved photoionization using an infrared pulse with a variable delay after the pair of excitation pulses. The photoelectron branching fractions and angular distributions display oscillations that depend on both the time delays and the relative phases of the VUV pulses. The combination of frequency, time delay, and phase selection provides significant control over the ionization process and ultimately improves the ability to analyze and assign complex molecular spectra.

Crystallization kinetics of atomic crystals revealed by a single-shot and single-particle X-ray diffraction experiment.

Crystallization is a fundamental natural phenomenon and the ubiquitous physical process in materials science for the design of new materials. So far, experimental observations of the structural dynamics in crystallization have been mostly restricted to slow dynamics. We present here an exclusive way to explore the dynamics of crystallization in highly controlled conditions (i.e., in the absence of impurities acting as seeds of the crystallites) as it occurs in vacuum. We have measured the early formation stage of solid Xe nanoparticles nucleated in an expanding supercooled Xe jet by means of an X-ray diffraction experiment with 10-fs X-ray free-electron laser (XFEL) pulses. We found that the structure of Xe nanoparticles is not pure face-centered cubic (fcc), the expected stable phase, but a mixture of fcc and randomly stacked hexagonal close-packed (rhcp) structures. Furthermore, we identified the instantaneous coexistence of the comparably sized fcc and rhcp domains in single Xe nanoparticles. The observations are explained by the scenario of structural aging, in which the nanoparticles initially crystallize in the highly stacking-disordered rhcp phase and the structure later forms the stable fcc phase. The results are reminiscent of analogous observations in hard-sphere systems, indicating the universal role of the stacking-disordered phase in nucleation.

Femtosecond Polarization Shaping of Free-Electron Laser Pulses.

We demonstrate the generation of extreme-ultraviolet (XUV) free-electron laser (FEL) pulses with time-dependent polarization. To achieve polarization modulation on a femtosecond timescale, we combine two mutually delayed counterrotating circularly polarized subpulses from two cross-polarized undulators. The polarization profile of the pulses is probed by angle-resolved photoemission and above-threshold ionization of helium; the results agree with solutions of the time-dependent Schrödinger equation. The stability limit of the scheme is mainly set by electron-beam energy fluctuations, however, at a level that will not compromise experiments in the XUV. Our results demonstrate the potential to improve the resolution and element selectivity of methods based on polarization shaping and may lead to the development of new coherent control schemes for probing and manipulating core electrons in matter.

Photochemical Ring-Opening Reaction of 1,3-Cyclohexadiene: Identifying the True Reactive State.

The photochemically induced ring-opening isomerization reaction of 1,3-cyclohexadiene to 1,3,5-hexatriene is a textbook example of a pericyclic reaction and has been amply investigated with advanced spectroscopic techniques. The main open question has been the identification of the single reactive state which drives the process. The generally accepted description of the isomerization pathway starts with a valence excitation to the lowest lying bright state, followed by a passage through a conical intersection to the lowest lying doubly excited state, and finally a branching between either the return to the ground state of the cyclic molecule or the actual ring-opening reaction leading to the open-chain isomer. Here, in a joint experimental and computational effort, we demonstrate that the evolution of the excitation-deexcitation process is much more complex than that usually described. In particular, we show that an initially high-lying electronic state smoothly decreasing in energy along the reaction path plays a key role in the ring-opening reaction.

Light-Induced Magnetization at the Nanoscale.

Triggering and switching magnetic moments is of key importance for applications ranging from spintronics to quantum information. A noninvasive ultrafast control at the nanoscale is, however, an open challenge. Here, we propose a novel laser-based scheme for generating atomic-scale charge current loops within femtoseconds. The associated orbital magnetic moments remain ferromagnetically aligned after the laser pulses have ceased and are localized within an area that is tunable via laser parameters and can be chosen to be well below the diffraction limit of the driving laser field. The scheme relies on tuning the phase, polarization, and intensities of two copropagating Gaussian and vortex laser pulses, allowing us to control the spatial extent, direction, and strength of the atomic-scale charge current loops induced in the irradiated sample upon photon absorption. In the experiment we used He atoms driven by an ultraviolet and infrared vortex-beam laser pulses to generate current-carrying Rydberg states and test for the generated magnetic moments via dichroic effects in photoemission. Ab initio quantum dynamic simulations and analysis confirm the proposed scenario and provide a quantitative estimate of the generated local moments.

Unravelling the full relaxation dynamics of superexcited helium nanodroplets.

The relaxation dynamics of superexcited superfluid He nanodroplets is thoroughly investigated by means of extreme-ultraviolet (XUV) femtosecond electron and ion spectroscopy complemented by time-dependent density functional theory (TDDFT). Three main paths leading to the emission of electrons and ions are identified: droplet autoionization, pump-probe photoionization, and autoionization induced by re-excitation of droplets relaxing into levels below the droplet ionization threshold. The most abundant product ions are He2+, generated by droplet autoionization and by photoionization of droplet-bound excited He atoms. He+ appear with some pump-probe delay as a result of the ejection He atoms in their lowest excited states from the droplets. The state-resolved time-dependent photoelectron spectra reveal that intermediate excited states of the droplets are populated in the course of the relaxation, terminating in the lowest-lying metastable singlet and triplet He atomic states. The slightly faster relaxation of the triplet state compared to the singlet state is in agreement with the simulation showing faster formation of a bubble around a He atom in the triplet state.

Carbon and Nitrogen K-Edge NEXAFS Spectra of Indole, 2,3-Dihydro-7-azaindole, and 3-Formylindole.

The near-edge X-ray absorption fine structure (NEXAFS) spectra of indole, 2,3-dihydro-7-azaindole, and 3-formylindole in the gas phase have been measured at the carbon and nitrogen K-edges. The spectral features have been interpreted based on density functional theory (DFT) calculations within the transition potential (TP) scheme, which is accurate enough for a general description of the measured C 1s NEXAFS spectra as well as for the assignment of the most relevant features. For the nitrogen K-edge, the agreement between experimental data and theoretical spectra calculated with TP-DFT was not quite satisfactory. This discrepancy was mainly attributed to the many-body effects associated with the excitation of the core electron, which are better described using the time-dependent density functional theory (TDDFT) with the range-separated hybrid functional CAM-B3LYP. An assignment of the measured N 1s NEXAFS spectral features has been proposed together with a complete description of the observed resonances. Intense transitions from core levels to unoccupied antibonding π* states as well as several transitions with mixed-valence/Rydberg or pure Rydberg character have been observed in the C and N K-edge spectra of all investigated indoles.

Time-resolved photoelectron imaging of complex resonances in molecular nitrogen.

We have used the FERMI free-electron laser to perform time-resolved photoelectron imaging experiments on a complex group of resonances near 15.38 eV in the absorption spectrum of molecular nitrogen, N2, under jet-cooled conditions. The new data complement and extend the earlier work of Fushitani et al. [Opt. Express 27, 19702-19711 (2019)], who recorded time-resolved photoelectron spectra for this same group of resonances. Time-dependent oscillations are observed in both the photoelectron yields and the photoelectron angular distributions, providing insight into the interactions among the resonant intermediate states. In addition, for most states, we observe an exponential decay of the photoelectron yield that depends on the ionic final state. This observation can be rationalized by the different lifetimes for the intermediate states contributing to a particular ionization channel. Although there are nine resonances within the group, we show that by detecting individual photoelectron final states and their angular dependence, we can identify and differentiate quantum pathways within this complex system.

High-gain harmonic generation with temporally overlapping seed pulses and application to ultrafast spectroscopy.

Collinear double-pulse seeding of the High-Gain Harmonic Generation (HGHG) process in a free-electron laser (FEL) is a promising approach to facilitate various coherent nonlinear spectroscopy schemes in the extreme ultraviolet (XUV) spectral range. However, in collinear arrangements using a single nonlinear medium, temporally overlapping seed pulses may introduce nonlinear mixing signals that compromise the experiment at short time delays. Here, we investigate these effects in detail by extending the analysis described in a recent publication (Wituschek et al., Nat. Commun., 11, 883, 2020). High-order fringe-resolved autocorrelation and wave packet interferometry experiments at photon energies > 23 eV are performed, accompanied by numerical simulations. It turns out that both the autocorrelation and the wave-packet interferometry data are very sensitive to saturation effects and can thus be used to characterize saturation in the HGHG process. Our results further imply that time-resolved spectroscopy experiments are feasible even for time delays smaller than the seed pulse duration.

Time-resolved formation of excited atomic and molecular states in XUV-induced nanoplasmas in ammonia clusters.

High intensity XUV radiation from a free-electron laser (FEL) was used to create a nanoplasma inside ammonia clusters with the intent of studying the resulting electron-ion interactions and their interplay with plasma evolution. In a plasma-like state, electrons with kinetic energy lower than the local collective Coulomb potential of the positive ionic core are trapped in the cluster and take part in secondary processes (e.g. electron-impact excitation/ionization and electron-ion recombination) which lead to subsequent excited and neutral molecular fragmentation. Using a time-delayed UV laser, the dynamics of the excited atomic and molecular states are probed from -0.1 ps to 18 ps. We identify three different phases of molecular fragmentation that are clearly distinguished by the effect of the probe laser on the ionic and electronic yield. We propose a simple model to rationalize our data and further identify two separate channels leading to the formation of excited hydrogen.

Experimental and Theoretical Photoemission Study of Indole and Its Derivatives in the Gas Phase.

The valence and core-level photoelectron spectra of gaseous indole, 2,3-dihydro-7-azaindole, and 3-formylindole have been investigated using VUV and soft X-ray radiation supported by both an ab initio electron propagator and density functional theory calculations. Three methods were used to calculate the outer valence band photoemission spectra: outer valence Green function, partial third order, and renormalized partial third order. While all gave an acceptable description of the valence spectra, the last method yielded very accurate agreement, especially for indole and 3-formylindole. The carbon, nitrogen, and oxygen 1s core-level spectra of these heterocycles were measured and assigned. The double ionization appearance potential for indole has been determined to be 21.8 ± 0.2 eV by C 1s and N 1s Auger photoelectron spectroscopy. Theoretical analysis identifies the doubly ionized states as a band consisting of two overlapping singlet states and one triplet state with dominant configurations corresponding to holes in the two uppermost molecular orbitals. One of the singlet states and the triplet state can be described as consisting largely of a single configuration, but other doubly ionized states are heavily mixed by configuration interactions. This work provides full assignment of the relative binding energies of the core level features and an analysis of the electronic structure of substituted indoles in comparison with the parent indole.

Fast beam monitor diamond-based devices for VUV and X-ray synchrotron radiation applications.

The improved performance of third-generation light sources and the advent of next-generation synchrotron radiation facilities require the use of extremely precise monitoring of the main photon-beam parameters, such as position, absolute and relative intensity, and temporal structure. These parameters, and associated real-time feedbacks, are fundamental at the beamline control level and at the machine control level, to improve the stability of the photon beams and to provide bunch-to-bunch quantitative information. Fast response time, high radiation hardness and visible-blind response are main features of photon-beam monitors for VUV and X-ray synchrotron radiation beamlines; hence diamond-based detectors are outstanding candidates. Here, results are presented of an extensive measurement campaign aiming at optimizing the capabilities of diamond detectors to discern time structures below the 100 ps timescale. A custom-built device has been fabricated and tested at the Italian Synchrotron Radiation Laboratory Elettra in Trieste. The results obtained show that diamond is an excellent material for ultra-fast photon pulses with picosecond time resolution; finally the possibilities for application at free-electron laser sources are discussed.

Complete Characterization of Phase and Amplitude of Bichromatic Extreme Ultraviolet Light.

Intense, mutually coherent beams of multiharmonic extreme ultraviolet light can now be created using seeded free-electron lasers, and the phase difference between harmonics can be tuned with attosecond accuracy. However, the absolute value of the phase is generally not determined. We present a method for determining precisely the absolute phase relationship of a fundamental wavelength and its second harmonic, as well as the amplitude ratio. Only a few easily calculated theoretical parameters are required in addition to the experimental data.

Ultrafast Structural Dynamics of Nanoparticles in Intense Laser Fields.

Femtosecond laser pulses have opened new frontiers for the study of ultrafast phase transitions and nonequilibrium states of matter. In this Letter, we report on structural dynamics in atomic clusters pumped with intense near-infrared (NIR) pulses into a nanoplasma state. Employing wide-angle scattering with intense femtosecond x-ray pulses from a free-electron laser source, we find that highly excited xenon nanoparticles retain their crystalline bulk structure and density in the inner core long after the driving NIR pulse. The observed emergence of structural disorder in the nanoplasma is consistent with a propagation from the surface to the inner core of the clusters.

Ultra-Fast-VUV Photoemission Study of UV Excited 2-Nitrophenol.

The initial deactivation pathways of gaseous 2-nitrophenol excited at 268 nm were investigated by time-resolved photoelectron spectroscopy (TRPES) with femtosecond-VUV light, produced by a monochromatized high harmonic generation source. TRPES allowed us to obtain new, valuable experimental information about the ultrafast excited-state dynamics of 2-nitrophenol in the gas phase. In accord with recent ab initio on-the-fly nonadiabatic molecular dynamic simulations, our results validate the occurrence of an ultrafast intersystem crossing leading to an intermediate state that decays on a subpicosecond time scale with a branched mechanisms. Two decay pathways are experimentally observed. One probably involves proton transfer, leading to the most stable triplet aci-form of 2-nitrophenol; the second pathway may involve OH rotation. We propose that following intersystem crossing, an ultrafast fragmentation channel leading to OH or HONO loss could also be operative.

Three-Dimensional Shapes of Spinning Helium Nanodroplets.

A significant fraction of superfluid helium nanodroplets produced in a free-jet expansion has been observed to gain high angular momentum resulting in large centrifugal deformation. We measured single-shot diffraction patterns of individual rotating helium nanodroplets up to large scattering angles using intense extreme ultraviolet light pulses from the FERMI free-electron laser. Distinct asymmetric features in the wide-angle diffraction patterns enable the unique and systematic identification of the three-dimensional droplet shapes. The analysis of a large data set allows us to follow the evolution from axisymmetric oblate to triaxial prolate and two-lobed droplets. We find that the shapes of spinning superfluid helium droplets exhibit the same stages as classical rotating droplets while the previously reported metastable, oblate shapes of quantum droplets are not observed. Our three-dimensional analysis represents a valuable landmark for clarifying the interrelation between morphology and superfluidity on the nanometer scale.

Impulsive laser-induced alignment of OCS molecules at FERMI.

We demonstrate the experimental realization of impulsive alignment of carbonyl sulfide (OCS) molecules at the Low Density Matter Beamline (LDM) at the free-electron laser FERMI. OCS molecules in a molecular beam were impulsively aligned using 200 fs pulses from a near-infrared laser. The alignment was probed through time-delayed ionization above the sulphur 2p edge, resulting in multiple ionization via Auger decay and subsequent Coulomb explosion of the molecules. The ionic fragments were collected using a time-of-flight mass spectrometer and the analysis of ion-ion covariance maps confirmed the correlation between fragments after Coulomb explosion. The analysis of the CO+ and S+ channels allowed us to extract the rotational dynamics, which is in agreement with our theoretical description as well as with previous experiments. This result opens the way for a new class of experiments at LDM within the field of coherent control of molecules with the possibilities that a precisely synchronized optical-pump XUV-probe laser setup like FERMI can offer.

The Low Density Matter (LDM) beamline at FERMI: optical layout and first commissioning.

The Low Density Matter (LDM) beamline has been built as part of the FERMI free-electron laser (FEL) facility to serve the atomic, molecular and cluster physics community. After the commissioning phase, it received the first external users at the end of 2012. The design and characterization of the LDM photon transport system is described, detailing the optical components of the beamline.