Bruce S. Rude

A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator

We discuss the construction of a new SAXS/WAXS beamline at the Advanced Light Source at Lawrence Berkeley Laboratory. The beamline is equipped with a multilayer monochromator in order to obtain a high X-ray flux. The detrimental effects that the increased bandwidth transmitted by this monochromator could have on the data quality of the SAXS and WAXS patterns is shown to be negligible for the experimental program intended to be operated on this beamline.

Surface relaxation in liquid water and methanol studied by x-ray absorption spectroscopy

X-ray absorption spectroscopy is a powerful probe of local electronic structure in disordered media. By employing extended x-ray absorption fine structure spectroscopy of liquid microjets, the intermolecular O–O distance has been observed to undergo a 5.9% expansion at the liquid water interface, in contrast to liquid methanol for which there is a 4.6% surface contraction. Despite the similar properties of liquid water and methanol (e.g., abnormal heats of vaporization, boiling points, dipole moments, etc.), this result implies dramatic differences in the surface hydrogen bond structure, which is evidenced by the difference in surface tension of these liquids. This result is consistent with surface vibrational spectroscopy, which indicates both stronger hydrogen bonding and polar ordering at the methanol surface as a consequence of “hydrophobic packing” of the methyl group.

Investigation of volatile liquid surfaces by synchrotron x-ray spectroscopy of liquid microjets

Soft x-ray absorption spectroscopy is a powerful probe of surface electronic and geometric structure in metals, semiconductors, and thin films. Because these techniques generally require ultrahigh vacuum, corresponding studies of volatile liquid surfaces have hitherto been precluded. We describe the design and implementation of an x-ray experiment based on the use of liquid microjets, permitting the study of volatile liquid surfaces under quasi-equilibrium conditions by synchrotron-based spectroscopy. The liquid microjet temperatures are also characterized by Raman spectroscopy, which connects our structural studies with those conducted on liquid samples under equilibrium conditions. In recent experiments, we have observed and quantified the intermolecular surface relaxation of liquid water and methanol and have identified a large population of “acceptor-only” molecules at the liquid water interface.

Characterization of hydrogen bond acceptor molecules at the water surface using near-edge x-ray absorption fine-structure spectroscopy and density functional theory

We present a combined experimental/computational study of the near-edge x-ray absorption fine structure of the liquid water surface which indicates that molecules with acceptor-only hydrogen bonding configurations constitute an important and previously unidentified component of the liquid/vapour interface.

Direct observation of Young’s double-slit interferences in vibrationally resolved photoionization of diatomic molecules

Vibrationally resolved valence-shell photoionization spectra of H2, N2 and CO have been measured in the photon energy range 20–300 eV using third-generation synchrotron radiation. Young’s double-slit interferences lead to oscillations in the corresponding vibrational ratios, showing that the molecules behave as two-center electron-wave emitters and that the associated interferences leave their trace in the angle-integrated photoionization cross section. In contrast to previous work, the oscillations are directly observable in the experiment, thereby removing any possible ambiguity related to the introduction of external parameters or fitting functions. A straightforward extension of an original idea proposed by Cohen and Fano [Cohen HD, Fano U (1966) Phys Rev 150:30] confirms this interpretation and shows that it is also valid for diatomic heteronuclear molecules. Results of accurate theoretical calculations are in excellent agreement with the experimental findings.

Monitoring chemical reactions at a liquid–solid interface: Water on CuIn(S,Se)2 thin film solar cell absorbers

The chemical and electronic structure of the interface between liquid water and a CuIn(S,Se)2 thin film surface was studied with synchrotron-based, high energy-resolution soft x-ray emission spectroscopy (XES). By probing the local environment around the sulfur atoms, an x-ray-induced sulfate formation at the CuIn(S,Se)2 surface can be monitored, correlated with a substantial enhancement of sodium impurity atoms from the CuIn(S,Se)2 film and its glass substrate. The results demonstrate that, with XES, an experimental probe is available to in situ study chemical reactions at liquid–solid interfaces or at surfaces in a high-pressure gas environment in a chemically sensitive and atom-specific way.

Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources

An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with the retarding ratio can be well approximated by applying Liouvilles theorem of constant emittance to the electron trajectories inside the lens system. The performance of the setup is demonstrated by characterizing the laser fluence-dependent transient surface photovoltage response of a laser-excited Si(100) sample.

Photoionization of ions of the nitrogen isoelectronic sequence: experiment and theory for F2+ and Ne3+

Absolute photoionization measurements are reported for admixtures of the ground and metastable states of F2+ from 56.3 eV to 75.6 eV, and of Ne3+ from 89.3 eV to 113.8 eV. The 4So ground-state and the 2Do and 2Po metastable-state fractions present in the primary ion beams were estimated from photoion yield measurements near their respective threshold energies. Most of the observed resonance structure has been spectroscopically assigned. The measurements are compared with new R-matrix theoretical calculations and with those in the TOPbase astrophysical database. The systematic behaviour of the quantum-defect parameter is analysed as a function of the nuclear charge for four Rydberg series observed in both species, and compared to published data for O+ and N.

Nitrogen isotopic fractionations in the low temperature (80 K) vacuum ultraviolet photodissociation of N2

N2 is a diatomic molecule with complex electronic structure. Interstate crossings are prominent in the high energy domain, introducing significant perturbations to the system. Nitrogen mainly photodissociates in the vacuum ultraviolet (VUV) region of the electromagnetic spectrum through both direct and indirect predissociation. Due to the complexity introduced by these perturbations, the nitrogen isotopic fractionation in N2 photodissociation is extremely hard to calculate, and an experimental approach is required. Here we present new data of N-isotopic fractionation in N2 photodissociation at low temperature (80 K), which shows a distinctly different 15N enrichment profile compared to that at relatively higher temperatures (200 and 300 K). The new data, important to understanding the N-isotopic compositions measured in meteorites and other planetary bodies, are discussed in light of the knowledge of N2 photochemistry and calculated photoabsorption cross sections in the VUV.

Photoionization of Xenon Clusters

High resolution photoelectron spectra of xenon clusters of about 100 atoms, measured with photon energies of 20 to 60 eV are reported. Peaks due to the clusters are observed at lower binding energies than the corresponding atomic lines and exhibit different behaviors. The peak associated with the Xe 5p1/2 state at higher binding energy is relatively unchanged with photon energy whereas the Xe 5p3/2 peak changes its shape with increasing photon energy. The change is attributed to differences in the escape depth of the electrons at different kinetic energies and the bulk and surface components of the cluster.