Influence of Selective Carbon 1s Excitation on Auger-Meitner Decay in the ESCA Molecule.

Two-dimensional spectral mapping is used to visualize how resonant Auger-Meitner spectra are influenced by the site of the initial core-electron excitation and the symmetry of the core-excited state in the trifluoroethyl acetate molecule (ESCA). We observe a significant enhancement of electron yield for excitation of the COO 1s → π* and CF3 1s → σ* resonances unlike excitation at resonances involving the CH3 and CH2 sites. The CF3 1s → π* and CF3 1s → σ* resonance spectra are very different from each other, with the latter populating most valence states equally. Two complementary electronic structure calculations for the photoelectron cross section and Auger-Meitner intensity are shown to effectively reproduce the site- and state-selective nature of the resonant enhancement features. The site of the core-electron excitation and the respective final state hole locality increase the sensistivity of the photoelectron signal at specific functional group sites. This showcases resonant Auger-Meitner decay as a potentially powerful tool for selectively probing structural changes at specific functional group sites of polyatomic molecules.

Resonant Inelastic X-Ray Scattering Reveals Hidden Local Transitions of the Aqueous OH Radical.

Resonant inelastic x-ray scattering (RIXS) provides remarkable opportunities to interrogate ultrafast dynamics in liquids. Here we use RIXS to study the fundamentally and practically important hydroxyl radical in liquid water, OH(aq). Impulsive ionization of pure liquid water produced a short-lived population of OH(aq), which was probed using femtosecond x-rays from an x-ray free-electron laser. We find that RIXS reveals localized electronic transitions that are masked in the ultraviolet absorption spectrum by strong charge-transfer transitions-thus providing a means to investigate the evolving electronic structure and reactivity of the hydroxyl radical in aqueous and heterogeneous environments. First-principles calculations provide interpretation of the main spectral features.

Observation of the fastest chemical processes in the radiolysis of water.

Elementary processes associated with ionization of liquid water provide a framework for understanding radiation-matter interactions in chemistry and biology. Although numerous studies have been conducted on the dynamics of the hydrated electron, its partner arising from ionization of liquid water, H2O+, remains elusive. We used tunable femtosecond soft x-ray pulses from an x-ray free electron laser to reveal the dynamics of the valence hole created by strong-field ionization and to track the primary proton transfer reaction giving rise to the formation of OH. The isolated resonance associated with the valence hole (H2O+/OH) enabled straightforward detection. Molecular dynamics simulations revealed that the x-ray spectra are sensitive to structural dynamics at the ionization site. We found signatures of hydrated-electron dynamics in the x-ray spectrum.

Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics.

New capabilities at X-ray free-electron laser facilities allow the generation of two-colour femtosecond X-ray pulses, opening the possibility of performing ultrafast studies of X-ray-induced phenomena. Particularly, the experimental realization of hetero-site-specific X-ray-pump/X-ray-probe spectroscopy is of special interest, in which an X-ray pump pulse is absorbed at one site within a molecule and an X-ray probe pulse follows the X-ray-induced dynamics at another site within the same molecule. Here we show experimental evidence of a hetero-site pump-probe signal. By using two-colour 10-fs X-ray pulses, we are able to observe the femtosecond time dependence for the formation of F ions during the fragmentation of XeF2 molecules following X-ray absorption at the Xe site.

Solvation dynamics monitored by combined X-ray spectroscopies and scattering: photoinduced spin transition in aqueous [Fe(bpy)3](2+).

We have studied the photoinduced low spin (LS) to high spin (HS) conversion of aqueous Fe(bpy)3 with pulse-limited time resolution. In a combined setup permitting simultaneous X-ray diffuse scattering (XDS) and spectroscopic measurements at a MHz repetition rate we have unraveled the interplay between intramolecular dynamics and the intermolecular caging solvent response with 100 ps time resolution. On this time scale the ultrafast spin transition including intramolecular geometric structure changes as well as the concomitant bulk solvent heating process due to energy dissipation from the excited HS molecule are long completed. The heating is nevertheless observed to further increase due to the excess energy between HS and LS states released on a subnanosecond time scale. The analysis of the spectroscopic data allows precise determination of the excited population which efficiently reduces the number of free parameters in the XDS analysis, and both combined permit extraction of information about the structural dynamics of the first solvation shell.

Guest-host interactions investigated by time-resolved X­ray spectroscopies and scattering at MHz rates: solvation dynamics and photoinduced spin transition in aqueous Fe(bipy)3(2+).

We have studied the photoinduced low spin (LS) to high spin (HS) conversion of [Fe(bipy)(3)](2+) in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate, we observed the interplay between intramolecular dynamics and the intermolecular caging solvent response with better than 100 ps time resolution. On this time scale, the initial ultrafast spin transition and the associated intramolecular geometric structure changes are long completed, as is the solvent heating due to the initial energy dissipation from the excited HS molecule. Combining information from X-ray emission spectroscopy and scattering, the excitation fraction as well as the temperature and density changes of the solvent can be closely followed on the subnanosecond time scale of the HS lifetime, allowing the detection of an ultrafast change in bulk solvent density. An analysis approach directly utilizing the spectroscopic data in the XDS analysis effectively reduces the number of free parameters, and both combined permit extraction of information about the ultrafast structural dynamics of the caging solvent, in particular, a decrease in the number of water molecules in the first solvation shell is inferred, as predicted by recent theoretical work.

Explosions of xenon clusters in ultraintense femtosecond x-ray pulses from the LCLS free electron laser.

Explosions of large Xe clusters ( ~ 11,000) irradiated by femtosecond pulses of 850 eV x-ray photons focused to an intensity of up to 10(17) W/cm(2) from the Linac Coherent Light Source were investigated experimentally. Measurements of ion charge-state distributions and energy spectra exhibit strong evidence for the formation of a Xe nanoplasma in the intense x-ray pulse. This x-ray produced Xe nanoplasma is accompanied by a three-body recombination and hydrodynamic expansion. These experimental results appear to be consistent with a model in which a spherically exploding nanoplasma is formed inside the Xe cluster and where the plasma temperature is determined by photoionization heating.

Angle-resolved electron spectroscopy of laser-assisted Auger decay induced by a few-femtosecond x-ray pulse.

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.

Unveiling and driving hidden resonances with high-fluence, high-intensity x-ray pulses.

We show that high fluence, high-intensity x-ray pulses from the world's first hard x-ray free-electron laser produce nonlinear phenomena that differ dramatically from the linear x-ray-matter interaction processes that are encountered at synchrotron x-ray sources. We use intense x-ray pulses of sub-10-fs duration to first reveal and subsequently drive the 1s↔2p resonance in singly ionized neon. This photon-driven cycling of an inner-shell electron modifies the Auger decay process, as evidenced by line shape modification. Our work demonstrates the propensity of high-fluence, femtosecond x-ray pulses to alter the target within a single pulse, i.e., to unveil hidden resonances, by cracking open inner shells energetically inaccessible via single-photon absorption, and to consequently trigger damaging electron cascades at unexpectedly low photon energies.

Nonlinear atomic response to intense ultrashort x rays.

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.

Femtosecond electronic response of atoms to ultra-intense X-rays.

An era of exploring the interactions of high-intensity, hard X-rays with matter has begun with the start-up of a hard-X-ray free-electron laser, the Linac Coherent Light Source (LCLS). Understanding how electrons in matter respond to ultra-intense X-ray radiation is essential for all applications. Here we reveal the nature of the electronic response in a free atom to unprecedented high-intensity, short-wavelength, high-fluence radiation (respectively 10(18) W cm(-2), 1.5-0.6 nm, approximately 10(5) X-ray photons per A(2)). At this fluence, the neon target inevitably changes during the course of a single femtosecond-duration X-ray pulse-by sequentially ejecting electrons-to produce fully-stripped neon through absorption of six photons. Rapid photoejection of inner-shell electrons produces 'hollow' atoms and an intensity-induced X-ray transparency. Such transparency, due to the presence of inner-shell vacancies, can be induced in all atomic, molecular and condensed matter systems at high intensity. Quantitative comparison with theory allows us to extract LCLS fluence and pulse duration. Our successful modelling of X-ray/atom interactions using a straightforward rate equation approach augurs favourably for extension to complex systems.

Attosecond synchronization of high-order harmonics from midinfrared drivers.

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.

Intense self-compressed, self-phase-stabilized few-cycle pulses at 2 microm from an optical filament.

We report the compression of intense, carrier-envelope phase stable mid-IR pulses down to few-cycle duration using an optical filament. A filament in xenon gas is formed by using self-phase stabilized 330 microJ 55 fs pulses at 2 microm produced via difference-frequency generation in a Ti:sapphire-pumped optical parametric amplifier. The ultrabroadband 2 microm carrier-wavelength output is self-compressed below 3 optical cycles and has a 270 microJ pulse energy. The self-locked phase offset of the 2 microm difference-frequency field is preserved after filamentation. This is to our knowledge the first experimental realization of pulse compression in optical filaments at mid-IR wavelengths (lambda>0.8 microm).

Probing hot and dense laser-induced plasmas with ultrafast XUV pulses.

In this Letter, we demonstrate the instantaneous creation of a hot solid-density plasma generated by focusing an intense femtosecond, high temporal contrast laser on an ultrathin foil (100 nm) in the 10(18) W/cm2 intensity range. The use of high-order harmonics generated in a gas jet, providing a probe beam of sufficiently short wavelengths to penetrate such a medium, enables the study of the dynamics of this plasma on the 100 fs time scale. The comparison of the transmission of two successive harmonics permits us to determine the electronic density and the temperature with accuracies better than 15%, never achieved up to this date in the regime of laser pulses at relativistic intensity.

Complete characterization of a plasma mirror for the production of high-contrast ultraintense laser pulses.

Improving the temporal contrast of ultrashort and ultraintense laser pulses is a major technical issue for high-field experiments. This can be achieved using a so-called "plasma mirror." We present a detailed experimental and theoretical study of the plasma mirror that allows us to quantitatively assess the performances of this system. Our experimental results include time-resolved measurements of the plasma mirror reflectivity, and of the phase distortions it induces on the reflected beam. Using an antireflection coated plate as a target, an improvement of the contrast ratio by more than two orders of magnitude can be achieved with a single plasma mirror. We demonstrate that this system is very robust against changes in the pulse fluence and imperfections of the beam spatial profile, which is essential for applications.