. Two-color, single-shot time-of-flight

We prove the hitherto hypothesized sequential dissociation of Fe(CO)5 in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)4 within the temporal resolution of the experiment and further to Fe(CO)3 within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)5, Fe(CO)4, and Fe(CO)3 showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)5 complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes.

Deploying the so-called `Streaking Spectroscopy' technique at LCLS, we demonstrate a non-invasive scheme for temporal characterization of X-ray pulses with sub-femtosecond resolution. Analyzing the substructure indicates pulse durations on the order of hundreds of attoseconds.

Short-wavelength free-electron lasers are now well established as essential and unrivalled sources of ultrabright coherent X-ray radiation. One of the key characteristics of these intense X-ray pulses is their expected few-femtosecond duration. No measurement has succeeded so far in directly determining the temporal structure or even the duration of these ultrashort pulses in the few-femtosecond range. Here, by deploying the so-called streaking spectroscopy technique at the Linac Coherent Light Source, we demonstrate a non-invasive scheme for temporal characterization of X-ray pulses with sub-femtosecond resolution. This method is independent of photon energy, decoupled from machine parameters, and provides an upper bound on the X-ray pulse duration. We measured the duration of the shortest X-ray pulses currently available to be on average no longer than 4.4 fs. Analysing the pulse substructure indicates a small percentage of the free-electron laser pulses consisting of individual high-intensity spikes to be on the order of hundreds of attoseconds.

The angular distribution of photoelectrons ejected during the ionization of Ne atoms by extreme ultraviolet (XUV) free-electron laser radiation in the presence of an intense near infrared (NIR) dressing field was investigated experimentally and theoretically. A highly nonlinear process with absorption and emission of more than ten NIR photons results in the formation of numerous sidebands. The amplitude of the sidebands varies strongly with the emission angle and the angular distribution pattern reveals clear signatures of interferences between the different angular momenta for the outgoing electron in the multi-photon process. As a specific feature, the central photoelectron line is characterized at the highest NIR fields by an angular distribution, which is peaked perpendicularly to both the XUV and NIR polarization directions. Experimental results are reproduced by a theoretical model based on the strong field approximation.

Two-color (x-ray+infrared) electron spectroscopy is used for investigating laser-assisted KLL Auger decay following 1s photoionization of atomic Ne with few-femtosecond x-ray pulses from the Linac Coherent Light Source. In an angle-resolved experiment, the overall width of the laser-modified Auger-electron spectrum and its structure change significantly as a function of the emission angle. The spectra are characterized by a strong intensity variation of the sidebands revealing a gross structure. This variation is caused, as predicted by theory, by the interference of electrons emitted at different times within the duration of one optical cycle of the infrared dressing laser, which almost coincides with the lifetime of the Ne 1s vacancy.

We present a systematic study of the photoionization of noble gas atoms exposed simultaneously to ultrashort (20 fs) monochromatic (1–2% spectral width) extreme ultraviolet (XUV) radiation from the Free-electron Laser in Hamburg (FLASH) and to intense synchronized near-infrared (NIR) laser pulses with intensities up to about 1013 W cm−2. Already at modest intensities of the NIR dressing field, the XUV-induced photoionization lines are split into a sequence of peaks due to the emission or absorption of several additional infrared photons. We observed a plateau-shaped envelope of the resulting sequence of sidebands that broadens with increasing intensity of the NIR dressing field. All individual lines of the nonlinear two-color ionization process are Stark-shifted, reflecting the effective intensity of the NIR field. The intensity-dependent cut-off energies of the sideband plateau are in good agreement with a classical model. The detailed structure of the two-color spectra, including the formation of individual sidebands, the Stark shifts and the contributions beyond the classical cut-off, however, requires a fully quantum mechanical description, as is demonstrated with time-dependent quantum calculations in single-active electron approximation.

The influence of an intense optical laser on the electronic relaxation of the 3d-5p resonance in atomic Kr has been studied experimentally and theoretically. The resonance profile undergoes a strong modification, observed as a shift and a broadening of the excitation spectrum, as a function of the optical intensity. The theoretical treatment of the process demonstrates the importance of strongly time-dependent dynamics as the origin of the observed phenomena resulting in the ponderomotive shift of the resonance position as well as a competition between resonant and normal Auger decay. The ionization of the excited 5p electron by the optical laser provides the possibility to change the ratio between singly and doubly charged final states by controlling the relaxation of the resonant core hole state via resonant or normal Auger decay.

The ability to fully characterize ultrashort, ultra-intense X-ray pulses at free-electron lasers (FELs) will be crucial in experiments ranging from single-molecule imaging to extreme-timescale X-ray science. This issue is especially important at current-generation FELs, which are primarily based on self-amplified spontaneous emission and radiate with parameters that fluctuate strongly from pulse to pulse. Using single-cycle terahertz pulses from an optical laser, we have extended the streaking techniques of attosecond metrology to measure the temporal profile of individual FEL pulses with 5 fs full-width at half-maximum accuracy, as well as their arrival on a time base synchronized to the external laser to within 6 fs r.m.s. Optical laser-driven terahertz streaking can be utilized at any X-ray photon energy and is non-invasive, allowing it to be incorporated into any pump–probe experiment, eventually characterizing pulses before and after interaction with most sample environments.

Argon gas at a high pressure (∼80 bar) has been expanded using a miniaturized pulsed valve at room temperature, producing a supersonic beam of cold, large argon droplets. Atoms of silver are subsequently embedded into the droplet using the pick-up technique. The resulting Ag(n)Ar(droplet) distribution was analyzed using multiphoton laser ionization time-of-flight mass spectrometry. Besides bare metal clusters, snowballs of silver monomers and dimers encapsulated in up to 50 argon atoms have been observed. The influence of the solvent on the optical absorption of the solute was studied for embedded Ag(8) using resonant two-photon ionization in the ultraviolet. A redshift and broadening of the Ag(8)Ar(droplet) optical spectrum compared to that measured in pure [Federmann et al., Eur. Phys. J. D 1999, 9, 11] and Ar-doped helium droplets [Diederich et al., J. Chem. Phys.2002, 116, 3263] was observed, which is attributed to the interaction with the larger Ar matrix environment.

Two-color, single-shot time-of-flight electron spectroscopy of atomic neon was employed at the Linac Coherent Light Source (LCLS) to measure laser-assisted Auger decay in the x-ray regime. This x-ray-optical cross-correlation technique provides a straightforward, non-invasive and on-line means of determining the duration of femtosecond (>40 fs) x-ray pulses. In combination with a theoretical model of the process based on the soft-photon approximation, we were able to obtain the LCLS pulse duration and to extract a mean value of the temporal jitter between the optical pulses from a synchronized Ti-sapphire laser and x-ray pulses from the LCLS. We find that the experimentally determined values are systematically smaller than the length of the electron bunches. Nominal electron pulse durations of 175 and 75 fs, as provided by the LCLS control system, yield x-ray pulse shapes of 120 +/- 20 fs full-width at half-maximum (FWHM) and an upper limit of 40 +/- 20 fs FWHM, respectively. Simulations of the free-electron laser agree well with the experimental results.

We report on the simultaneous determination of non-linear dispersion functions and resolving power of three flat-field XUV grating spectrometers. A moderate-intense short-pulse infrared laser is focused onto technical aluminum which is commonly present as part of the experimental setup. In the XUV wavelength range of 10–19 nm, the spectrometers are calibrated using Al-Mg plasma emission lines. This cross-calibration is performed in-situ in the very same setup as the actual main experiment. The results are in excellent agreement with ray-tracing simulations. We show that our method allows for precise relative and absolute calibration of three different XUV spectrometers.

The development of high power, infra-red (IR) femtosecond l asers has uncovered a rich vein of non-perturbative phenomena in the bound-free and free-fre e transitions of atoms interacting with coherent light. It is atstrong-fieldintensities at and above 10 W/cm that such behavior produces above threshold ionization (ATI), high-harmonic gen eration (HHG), and attosecond pulse generation [1, 2, 3]. The combination of extreme ultraviole t (XUV) and IR photons represents a particularly powerful method for the study of continuum tra nsitions since the bound-free step can be made insensitive to atomic resonances by appropriate pho ton energy tuning or selection. We have studied the response of atomic neon exposed simultaneo usly t intense monochromatic XUV radiation from the free electron laser in Hamburg (FLASH) an d synchronized IR laser. Already at modest intensities the main photoelectron line is striki ngly modulated by the IR dressing field, producing strong sideband features in the electron energy s pectrum. As a precursor to more elaborate quantum mechanical calculations a classical model wa s considered, which reproduces the characteristics of the two-color signal at high intensitie in a satisfactory manner.

X-ray scattering using highly brilliant x-ray free-electron laser (FEL) radiation provides new access to probe free-electron density, temperature and ionization in near-solid density plasmas. First experiments at the soft x-ray FEL FLASH at DESY, Hamburg, show the capabilities of this technique. The ultrashort FEL pulses in particular can probe equilibration phenomena occurring after excitation of the plasma using ultrashort optical laser pumping. We have investigated liquid hydrogen and find that the interaction of very intense soft x-ray FEL radiation alone heats the sample volume. As the plasma establishes, photons from the same pulse undergo scattering, thus probing the transient, warm dense matter state. We find a free-electron density of (2.6 ± 0.2) × 1020 cm−3 and an electron temperature of 14 ± 3.5 eV. In pump–probe experiments, using intense optical laser pulses to generate more extreme states of matter, this interaction of the probe pulse has to be considered in the interpretation of scattering data. In this paper, we present details of the experimental setup at FLASH and the diagnostic methods used to quantitatively analyse the data.

We report on soft X-ray scattering experiments on cryogenic hydrogen and simple metal samples. As a source of intense, ultrashort soft X-ray pulses we have used free-electron laser radiation at 92 eV photon energy from FLASH at DESY, Hamburg. X-ray pulses with energies up to 150 μJ and durations 15–50 fs provide interaction with the sample leading simultaneously to plasma formation and scattering. Experiments exploiting both of these interactions have been carried out, using the same experimental setup. Firstly, recording of soft X-ray inelastic scattering from near-solid density hydrogen plasmas at few electron volt temperatures confirms the feasibility of this diagnostics technique. Secondly, the soft X-ray excitation of few electron volt solid-density plasmas in bulk metal samples could be studied by recording soft X-ray line and continuum emission integrated over emission times from fs to ns.

Two-photon excitation of a single-photon forbidden Auger resonance has been observed and investigated using the intense extreme ultraviolet radiation from the free electron laser in Hamburg. At the wavelength 26.9 nm (46 eV) two photons promoted a 3d core electron to the outer 4d shell. The subsequent Auger decay, as well as several nonlinear above threshold ionization processes, were studied by electron spectroscopy. The experimental data are in excellent agreement with theoretical predictions and analysis of the underlying multiphoton processes.

The advent of free electron laser (FEL) facilities capable of delivering high intensity pulses in the extreme-UV to X-ray spectral range has opened up a wide vista of opportunities to study and control light matter interactions in hitherto unexplored parameter regimes. In particular, current short wavelength FELs can uniquely drive non-linear processes mediated by inner shell electrons and in fields where the photon energy can be as high as 10 keV and so the corresponding optical period reaches below one attosecond. Combined with ultrafast optical lasers, or simply employing wavefront division, pump probe experiments can be performed with femtosecond time resolution. As single photon ionization of atoms and molecules is by now very well understood, they provide the ideal targets for early experiments by which not only FELs can be characterised and benchmarked but can also be the natural departure point in the hunt for non-linear behaviour of atomistic systems bathed in laser fields of ultrahigh photon energy. In this topical review we illustrate with specific examples the gamut of apposite experiments in atomic, molecular physics currently underway at the SCSS Test Accelerator (Japan), FLASH (Hamburg) and LCLS (Stanford).