Attosecond Photoionization Dynamics: from Molecules over Clusters to the Liquid Phase.

Photoionization is a process taking place on attosecond time scales. How its properties evolve from isolated particles to the condensed phase is an open question of both fundamental and practical relevance. Here, we review recent work that has advanced the study of photoionization dynamics from atoms to molecules, clusters and the liquid phase. The first measurements of molecular photoionization delays have revealed the attosecond dynamics of electron emission from a molecular shape resonance and their sensitivity to the molecular potential. Using electron-ion coincidence spectroscopy these measurements have been extended from isolated molecules to clusters. A continuous increase of the delays with the water-cluster size has been observed up to a size of 4-5 molecules, followed by a saturation towards larger clusters. Comparison with calculations has revealed a correlation of the time delay with the spatial extension of the created electron hole. Using cylindrical liquid-microjet techniques, these measurements have also been extended to liquid water, revealing a delay relative to isolated water molecules that was very similar to the largest water clusters studied. Detailed modeling based on Monte-Carlo simulations confirmed that these delays are dominated by the contributions of the first two solvation shells, which agrees with the results of the cluster measurements. These combined results open the perspective of experimentally characterizing the delocalization of electronic wave functions in complex systems and studying their evolution on attosecond time scales.

Photoelectron Spectroscopy of Liquid Water with Tunable Extreme-Ultraviolet Radiation: Effects of Electron Scattering.

We report the first systematic photoelectron measurements of the three outer-valence bands of liquid water as a function of the ionizing photon energy in the near-threshold region. We use extreme-ultraviolet (XUV) radiation tunable between ∼17.1 and 35.6 eV, obtained through monochromatization of a high-harmonic source. We show that the absolute values of the apparent vertical ionization energies and their respective peak widths show a decreasing trend of their magnitudes with increasing photon energy close to the ionization threshold. We find that the observed effects do not only depend on the electron kinetic energy but are also different for the various outer-valence bands. These observations are consistent with, but not fully explained by, the effects of inelastic electron scattering.

Attosecond spectroscopy of liquid water.

Electronic dynamics in liquids are of fundamental importance, but time-resolved experiments have so far remained limited to the femtosecond time scale. We report the extension of attosecond spectroscopy to the liquid phase. We measured time delays of 50 to 70 attoseconds between the photoemission from liquid water and that from gaseous water at photon energies of 21.7 to 31.0 electron volts. These photoemission delays can be decomposed into a photoionization delay sensitive to the local environment and a delay originating from electron transport. In our experiments, the latter contribution is shown to be negligible. By referencing liquid water to gaseous water, we isolated the effect of solvation on the attosecond photoionization dynamics of water molecules. Our methods define an approach to separating bound and unbound electron dynamics from the structural response of the solvent.

Ionization Energy of Liquid Water Revisited.

The ionization energy of liquid water is one of its most fundamental properties, an important benchmark for first-principles electronic-structure calculations and a crucial reference in the growing field of liquid-phase photoelectron spectroscopy. Despite this significance, a consensus on its value appears to be missing in the literature. Therefore, we use a monochromatized high-harmonic light source to perform detailed measurements of the ionization energy of liquid water in the presence of a tunable bias voltage applied to the liquid jet. Our results suggest that this simple method is sufficient to simultaneously compensate the effects of the streaming potential and that of the vacuum-level offset between the liquid and the photoelectron spectrometer. Our measurements yield corrected values of the vertical and adiabatic ionization energies of the 1b1 band of bulk liquid water of 11.67(15) and 10.12(15) eV, respectively. Our method is broadly applicable and is likely to result in corrections to the measured ionization energies of solvated species as well.

Photoelectron spectrometer for liquid and gas-phase attosecond spectroscopy with field-free and magnetic bottle operation modes.

A compact time-of-flight spectrometer for applications in attosecond spectroscopy in the liquid and gas phases is presented. It allows for altering the collection efficiency by transitioning between field-free and magnetic-bottle operation modes. High energy resolution (ΔE/E = 0.03 for kinetic energies >20 eV) is achieved despite the short flight-tube length through a homogeneous deceleration potential at the beginning of the flight tube. A closing mechanism allows isolating the vacuum system of the flight tube from the interaction region in order to efficiently perform liquid-microjet experiments. The capabilities of the instrument are demonstrated through photoelectron spectra from multiphoton ionization of argon and xenon, as well as photoelectron spectra of liquid and gaseous water generated by an attosecond pulse train.

Streaking of 43-attosecond soft-X-ray pulses generated by a passively CEP-stable mid-infrared driver.

Attosecond metrology has so far largely remained limited to titanium:sapphire lasers combined with an active stabilization of the carrier-envelope phase (CEP). These sources limit the achievable photon energy to ∼100 eV which is too low to access X-ray absorption edges of most second- and third-row elements which are central to chemistry, biology and material science. Therefore, intense efforts are underway to extend attosecond metrology to the soft-X-ray (SXR) domain using mid-infrared (mid-IR) drivers. Here, we introduce and experimentally demonstrate a method that solves the long-standing problem of the complete temporal characterization of ultra-broadband (≫10 eV) attosecond pulses. We generalize the recently proposed Volkov-transform generalized projection algorithm (VTGPA) to the case of multiple overlapping photoelectron spectra and demonstrate its application to isolated attosecond pulses. This new approach overcomes all key limitations of previous attosecond-pulse reconstruction methods, in particular the central-momentum approximation (CMA), and it incorporates the physical, complex-valued and energy-dependent photoionization matrix elements. These properties make our approach general and particularly suitable for attosecond supercontinua of arbitrary bandwidth. We apply this method to attosecond SXR pulses generated from a two-cycle mid-IR driver, covering a bandwidth of ∼100 eV and reaching photon energies up to 180 eV. We extract an SXR pulse duration of (43±1) as from our streaking measurements, defining a new world record. Our results prove that the popular and broadly available scheme of post-compressing the output of white-light-seeded optical parametric amplifiers is adequate to produce high-contrast isolated attosecond pulses covering the L-edges of silicon, phosphorous and sulfur. Our new reconstruction method and experimental results open the path to the production and characterization of attosecond pulses lasting less than one atomic unit of time (24 as) and covering X-ray absorption edges of most light elements.

Attosecond Delays in Molecular Photoionization.

We report measurements of energy-dependent photoionization delays between the two outermost valence shells of N_{2}O and H_{2}O. The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train enables us to extract delays from congested spectra. Remarkably large delays up to 160 as are observed in N_{2}O, whereas the delays in H_{2}O are all smaller than 50 as in the photon-energy range of 20-40 eV. These results are interpreted by developing a theory of molecular photoionization delays. The long delays measured in N_{2}O are shown to reflect the population of molecular shape resonances that trap the photoelectron for a duration of up to ∼110 as. The unstructured continua of H_{2}O result in much smaller delays at the same photon energies. Our experimental and theoretical methods make the study of molecular attosecond photoionization dynamics accessible.

In situ frequency gating and beam splitting of vacuum- and extreme-ultraviolet pulses.

Monochromatization of high-harmonic sources has opened fascinating perspectives regarding time-resolved photoemission from all phases of matter. Such studies have invariably involved the use of spectral filters or spectrally dispersive optical components that are inherently lossy and technically complex. Here we present a new technique for the spectral selection of near-threshold harmonics and their spatial separation from the driving beams without any optical elements. We discover the existence of a narrow phase-matching gate resulting from the combination of the non-collinear generation geometry in an extended medium, atomic resonances and absorption. Our technique offers a filter contrast of up to 104 for the selected harmonics against the adjacent ones and offers multiple temporally synchronized beamlets in a single unified scheme. We demonstrate the selective generation of 133, 80 or 56 nm femtosecond pulses from a 400-nm driver, which is specific to the target gas. These results open new pathways towards phase-sensitive multi-pulse spectroscopy in the vacuum- and extreme-ultraviolet, and frequency-selective output coupling from enhancement cavities.

Non-uniform spatial distribution of tin oxide (SnO2) nanoparticles at the air-water interface.

Depth resolved X-ray photoelectron spectroscopy (XPS) combined with a 25 µm liquid jet is used to quantify the spatial distribution of 3 nm SnO2 nanoparticles (NPs) from the air-water interface (AWI) into the suspension bulk. Results are consistent with those of a layer several nm thick at the AWI that is completely devoid of NPs.

A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions.

A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.