Olle Björneholm

Beam line I411 at MAX II - Performance and first results

We report on the characteristics and first results from the soft X-ray beam line I411, based on an undulator at the third generation synchrotron facility MAX II, Sweden. The beam line is designed for high-resolution, angle-resolved electron spectroscopy on gases, liquids and solids. Main components are the modified SX700 monochromator and the end station, both of which were previously used at beam line 51 at MAX I. The end station is equipped with a rotatable SES-200 hemispherical electron-analyser. Before the end station, a one-metre section is reserved for exchangeable experimental set-ups. The usable photon energy range is 50-1500 eV and the photon flux is two orders of magnitudes higher compared to beam line 51. At 400 eV a resolving power of about 5700 in the first order of the monochromator grating could be obtained. In gas phase, a total electron energy resolution of 16 meV has been achieved. Detailed results on the undulator performance, flux, photon and electron energy resolution as well as some technical details are presented here. As an example of the capabilities of the beam line I411, we present the fully vibrationally resolved Auger resonant Raman electron spectrum of gas-phase N 2.

Overlayer structure from adsorbate and substrate core level binding energy shifts: CO, CCH3 and O on Pt(111)

Abstract By combining high resolution photoemission measurements of adsorption induced binding energy shifts of both adsorbate and substrate core levels the nature and distribution of adsorption sites in the CO/Pt(111) system can be determined. The existence of different surface shifted components demonstrates the local character of the surface core level shift. This is used to study the O/Pt(111) (2 × 2) and CCH3/Pt(111) “(2 × 2)” phases. The intensity relations of the different surface peaks suggest O/Pt(111) to be a true (2 × 2) phase, while the CCH3/Pt(111) “(2 × 2)” phase is proposed to consist of three equivalent (2 × 1) domains.

Soft X-ray undulator beam line I411 at MAX-II for gases, liquids and solid samples

We report on the build-up of the new undulator beam line 1411 at the third-generation synchrotron radiation facility MAX II in Lund, Sweden. This beam line is based on an upgraded version of the modified SX700-monochromator and the end station which were installed previously at beam line 51 at MAX I. The end station is equipped with a rotatable Scienta hemispherical electron-analyser making angle-resolved high resolution electron spectroscopy possible for various kinds of samples. The beam line performance will be considerably improved on MAX II due to a new undulator and the superior light source properties, e.g. the small vertical electron beam size. Undulator spectra have been measured and estimates of the photon flux at the experiment and the expected energy resolution are presented. The parameters for a new refocusing mirror were defined by ray tracing using the beam waist of the undulator. The beam line length was extended by 1 m to offer additional space for exchangeable experimental chambers.

Water at Interfaces

The interfaces of neat water and aqueous solutions play a prominent role in many technological processes and in the environment. Examples of aqueous interfaces are ultrathin water films that cover most hydrophilic surfaces under ambient relative humidities, the liquid/solid interface which drives many electrochemical reactions, and the liquid/vapor interface, which governs the uptake and release of trace gases by the oceans and cloud droplets. In this article we review some of the recent experimental and theoretical advances in our knowledge of the properties of aqueous interfaces and discuss open questions and gaps in our understanding.

Evidence for ultra-fast dissociation of molecular water from resonant Auger spectroscopy

We present direct evidence for ultra-fast dissociation of molecular water in connection photo-excitation of the Ols --> 4a(1) resonance. The core-excited H2O molecules are shown to dissociate into core-excited O*H and neutral H on a time scale comparable

The electronic structure of free water clusters probed by Auger electron spectroscopy

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.

Orientation of a molecular precursor: a NEXAFS study of O2/Ag(110)

We present the results of a near-edge X-ray absorption fine structure (NEXAFS) study of physisorbed and chemisorbed molecular oxygen on Ag(110). The physisorbed species was found to lie down on the surface for the monolayer case (with a mean tilt of 29° ± 5° away from the surface) and with the molecular axis lying along the [001] direction; this is perpendicular to the conventionally held azimuthal orientation of the chemisorbed molecule. For the chemisorbed phase, our spectra show features not seen in earlier studies; these cannot be interpreted in terms of the orbitals of the free molecules and imply both the π and π∗ oxygen molecular orbitals are involved in bonding with the substrate.

Photoabsorption and the unoccupied partial density of states of chemisorbed molecules

The 1s to 2π* resonances have been studied for CO strongly chemisorbed on Ni(100) and weakly chemisorbed on Cu(100) using high resolution X-ray absorption spectroscopy. We show that the spectra can be consistently described in terms of the local density of unoccupied 2π* electron states with the Fermi level obtained from corresponding X-ray photoelectron spectra. The core hole is demonstrated to induce large shifts in the unoccupied 2π* density of states.

On the Origins of Core−Electron Chemical Shifts of Small Biomolecules in Aqueous Solution: Insights from Photoemission and ab Initio Calculations of Glycineaq

The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon 1s binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine.

Observation of resonant interatomic coulombic decay in Ne clusters.

We have measured the electron spectra of Ne clusters after excitation with photon energies around the 2s inner valence threshold. At two photon energies below threshold, a resonantly enhanced surplus of low kinetic-energy electrons is observed. The kinetic energy of the peak does not vary with the photon energy and is slightly larger than the transition energy of Interatomic Coulombic Decay (ICD) above threshold. This leads us to assume that an ICD-like process is present. In analogy to the Auger and the resonant Auger decay this new phenomenon is termed resonant ICD.