Intense X-ray free-electron lasers (XFELs) can rapidly excite matter, leaving it in inherently unstable states that decay on femtosecond timescales. As the relaxation occurs primarily via Auger emission, excited state observations are constrained by Auger decay. In situ measurement of this process is therefore crucial, yet it has thus far remained elusive at XFELs due to inherent timing and phase jitter, which can be orders of magnitude larger than the timescale of Auger decay. Here, we develop a new approach termed self-referenced attosecond streaking, based upon simultaneous measurements of streaked photo- and Auger electrons. Our technique enables sub-femtosecond resolution in spite of jitter. We exploit this method to make the first XFEL time-domain measurement of the Auger decay lifetime in atomic neon, and, by using a fully quantum-mechanical description, retrieve a lifetime of $2.2^{ + 0.2}_{ - 0.3}$ fs for the KLL decay channel. Importantly, our technique can be generalised to permit the extension of attosecond time-resolved experiments to all current and future FEL facilities.

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

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.

High harmonic generation (HHG) is used to measure the spectral phase of the recombination dipole matrix element (RDM) in argon over a broad frequency range that includes the 3p Cooper minimum (CM). The measured RDM phase agrees well with predictions based on the scattering phases and amplitudes of the interfering sand d-channel contributions to the complementary photoionization process. The reconstructed attosecond bursts that underlie the HHG process show that the derivative of the RDM spectral phase, the group delay, does not have a straight-forward interpretation as an emission time, in contrast to the usual attochirp group delay. Instead, the rapid RDM phase variation caused by the CM reshapes the attosecond bursts.

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.

X-ray free-electron lasers (FELs) produce femtosecond x-ray pulses with unprecedented intensities that are uniquely suited for studying many phenomena in atomic, molecular, and optical (AMO) physics. A compilation of the current developments at the Linac Coherent Light Source (LCLS) and future plans for the LCLS-II and Next Generation Light Source (NGLS) are outlined. The AMO instrumentation at LCLS and its performance parameters are summarized. A few selected experiments representing the rapidly developing field of ultra-fast and peak intensity x-ray AMO sciences are discussed. These examples include fundamental aspects of intense x-ray interaction with atoms, nonlinear atomic physics in the x-ray regime, double core-hole spectroscopy, quantum control experiments with FELs and ultra-fast x-ray induced dynamics in clusters. These experiments illustrate the fundamental aspects of the interaction of intense short pulses of x-rays with atoms, molecules and clusters that are probed by electron and ion spectroscopies as well as ultra-fast x-ray scattering.

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.

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.

The nonlinear absorption mechanisms of neon atoms to intense, femtosecond kilovolt x rays are investigated. The production of Ne(9+) is observed at x-ray frequencies below the Ne(8+), 1s(2) absorption edge and demonstrates a clear quadratic dependence on fluence. Theoretical analysis shows that the production is a combination of the two-photon ionization of Ne(8+) ground state and a high-order sequential process involving single-photon production and ionization of transient excited states on a time scale faster than the Auger decay. We find that the nonlinear direct two-photon ionization cross section is orders of magnitude higher than expected from previous calculations.

Nonlinear absorption of femtosecond kilovolt x-rays in Neon is investigated. A possible two-photon Ionization is observed with the presence of Ne9+ at photon energies below the Ne8+ 1s2 ionization threshold.

The group delay dispersion, also known as the attochirp, of high-order harmonics generated in gases has been identified as the main intrinsic limitation to the duration of Fourier-synthesized attosecond pulses. Theory implies that the attochirp, which is inversely proportional to the laser wavelength, can be decreased at longer wavelength. Here we report the first measurement of the wavelength dependence of the attochirp using an all-optical, in situ method [N. Dudovich, Nature Phys. 2, 781 (2006)10.1038/nphys434]. We show that a 2 microm driving wavelength reduces the attochirp with respect to 0.8 microm at comparable intensities.

The paper reviews recent advances in high harmonic generation from mid-infrared lasers. The results emphasize the advantages of long wavelength drivers for cut-off extension, GDD reduction, attosecond pulses and reports on below-threshold and liquid harmonics.