Inga Jordan

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.

Attosecond delays in molecular photoionization

We report measurements of energy-dependent attosecond photoionization delays between the two outermost valence shells of N2O and H2O and compare them to results from a state-of-the art theory [1]. The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train (see Fig. 1 (a) and (b)) enables us to extract delays from congested photoelectron spectra. The results are interpreted by comparing to calculated molecular photoionization delays.

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.

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.

Photoelectron spectrometer for attosecond spectroscopy of liquids and gases

A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectra for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup.

Attosecond beamline with actively stabilized and spatially separated beam paths

We describe a versatile and compact beamline for attosecond spectroscopy. The setup consists of a high-order harmonic source followed by a delay line that spatially separates and then recombines the extreme-ultraviolet (XUV) and residual infrared (IR) pulses. The beamline introduces a controlled and actively stabilized delay between the XUV and IR pulses on the attosecond time scale. A new active-stabilization scheme combining a helium-neon-laser and a white-light interferometer minimizes fluctuations and allows to control delays accurately (26 as rms during 1.5 h) over long time scales. The high-order-harmonic-generation region is imaged via optical systems, independently for XUV and IR, into an interaction volume to perform pump-probe experiments. As a consequence of the spatial separation, the pulses can be independently manipulated in intensity, polarization, and frequency content. The beamline can be combined with a variety of detectors for measuring attosecond dynamics in gases, liquids, and solids.

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.

Photoemission and photoionization time delays and rates

Ionization and, in particular, ionization through the interaction with light play an important role in fundamental processes in physics, chemistry, and biology. In recent years, we have seen tremendous advances in our ability to measure the dynamics of photo-induced ionization in various systems in the gas, liquid, or solid phase. In this review, we will define the parameters used for quantifying these dynamics. We give a brief overview of some of the most important ionization processes and how to resolve the associated time delays and rates. With regard to time delays, we ask the question: how long does it take to remove an electron from an atom, molecule, or solid? With regard to rates, we ask the question: how many electrons are emitted in a given unit of time? We present state-of-the-art results on ionization and photoemission time delays and rates. Our review starts with the simplest physical systems: the attosecond dynamics of single-photon and tunnel ionization of atoms in the gas phase. We then extend the discussion to molecular gases and ionization of liquid targets. Finally, we present the measurements of ionization delays in femto- and attosecond photoemission from the solid–vacuum interface.

Relativistic photoionization delays and the role of auto-ionizing resonances

We measured the relative ionization delays into the two spin-orbit components of the electronic ground states of Xe+ and Kr+ under the inuence of auto-ionizing intermediate and final states. The results are in good agreement with state-of-the-art calculations based on the time-dependent configuration-interaction singles (TDCIS) approach.