Modern X-ray spectroscopy:XAS and XES in the laboratory

X-ray spectroscopy is an important tool for scientific analysis. While the earliest demonstration experiments were realised in the laboratory, with the advent of synchrotron light sources most of the experiments shifted to large scale synchrotron facilities. In the recent past there is an increased interest to perform X-ray experiments also with in-house laboratory sources, to simplify access to X-ray absorption and X-ray emission spectroscopy, in particular for routine measurements. Here we summarise the recent developments and comment on the most representative example experiments in the field of in-house laboratory X-ray spectroscopy. We first give an introduction and some historic background on X-ray spectroscopy. This is followed by an overview of the detection techniques used for X-ray absorption and X-ray emission measurements. A short paragraph also puts related high energy resolution and resonant techniques into context, though they are not yet feasible in the laboratory. At the end of this section the opportunities using wavelength dispersive X-ray spectroscopy in the laboratory are discussed. Then we summarise the relevant details of the recent experimental laboratory setups split into two separate sections, one for the recent von Hamos setups, and one for the recent Johann/Johansson type setups. Following that, focussing on chemistry and catalysis, we then summarise some of the notable X-ray absorption and X-ray emission experiments and the results accomplished with in-house setups. In a third part we then discuss some applications of laboratory X-ray spectroscopy with a particular focus on chemistry and catalysis.</p

Free Clusters Studied by Synchrotron-Based X-ray Spectroscopy: From Rare Gases to Metals

The main topic of this Thesis is the x-ray spectroscopic studies of free nano-clusters with size more than 10^3 atoms. The photoelectron spectroscopy experiments on rare gas and metal clusters were performed at beamline I411 at MAX-lab National Swedish synchrotron radiation facility. Free rare-gas clusters are simplest objects in cluster research. However their electronic structure springs a lot of surprises. In the x-ray absorption spectra of free Kr clusters the positions of the related cluster and atomic states of the higher 3d^{-1}6p and 3d^{-1}7p excited states in bulk and surface atoms are reversed compared to the 3d^{-1}5p state. The energy shifts of the higher core-excited states in cluster atoms grow towards the limiting values of the core-ionized states. The knowledge of the final cluster states reached after Auger decay of the resonantly excited core states threw a new light on this phenomenon. We explain these experimental findings by a spatial spread of the excited orbitals over the cluster lattice. The interplay of the two main effects - confinement and polarization - leads to qualitatively different situations. When the excited orbital radius is less than the interatomic distance in clusters (3d^{-1}5p state in Kr), confinement dominates. If the excited orbital radius exceeds the nearest neighbour distance (3d^{-1}np, n>5 states in Kr), polarization takes over and the energy-level structure becomes ion-like. Interest in studies of more complex than rare gas clusters systems determined the construction of the gas-aggregation metal cluster source. For the vaporisation of low melting point metals (Na) an oven was used. Vapours of higher melting point metals (Ag, Cu, Pb) were produced with a magnetron sputtering source. The design of the gas-aggregation source and description of the experimental setup are presented in this Thesis. Using this source we performed the first core-level photoemission (XPS) experiments on free metal clusters. The recorded spectra have shown that synchrotron-based x-ray core-level photoelectron spectroscopy can be efficiently implemented to free metal clusters. The evolution of the electronic structure with size has been studied by valence ionization, XPS and Auger techniques. These measurements have shown a close similarity between large clusters and solids. The difference between the established ionization potential of metal clusters and the solid has been used for the cluster size estimation for Na, Cu and Ag clusters. The presence of neutral and charged metal clusters in the Pb cluster beam created by magnetron-based source has offered an independent method for estimating cluster dimensions from core-level spectra, in which the charge states are resolved

A Dispersive Inelastic X-ray Scattering Spectrometer for Use at X-ray Free Electron Lasers

We report on the application of a short working distance von Hamos geometry spectrometer to measure the inelastic X-ray scattering (IXS) signals from solids and liquids. In contrast to typical IXS instruments where the spectrometer geometry is fixed and the incoming beam energy is scanned, the von Hamos geometry allows measurements to be made using a fixed optical arrangement with no moving parts. Thanks to the shot-to-shot capability of the spectrometer setup, we anticipate its application for the IXS technique at X-ray free electron lasers (XFELs). We discuss the capability of the spectrometer setup for IXS studies in terms of efficiency and required total incident photon flux for a given signal-to-noise ratio. The ultimate energy resolution of the spectrometer, which is a key parameter for IXS studies, was measured to the level of 150 meV at short crystal radius thanks to the application of segmented crystals for X-ray diffraction. The short working distance is a key parameter for spectrometer efficiency that is necessary to measure weak IXS signals

Enhanced surface sensitivity in AES relative to XPS observed in free argon clusters

The surface-to-bulk intensity ratio in Auger electron spectra has been studied in comparison with core-level photoelectron spectra using free argon clusters of sizes ranging over two orders of magnitude. Enhanced surface sensitivity is observed in L2,3M2,3M2.3 Auger electron spectra compared to 2p photoelectron spectra where electrons of similar kinetic energies were recorded. This is discussed in terms of the effective attenuation length of the electrons

Ruthenium 4d-to-2p X-ray Emission Spectroscopy: A Simultaneous Probe of the Metal and the Bound Ligands

Ruthenium 4d-to-2p X-ray emission spectroscopy (XES) was systematically explored for a series of Ru$^{2+}$ and Ru$^{3+}$ species. Complementary density functional theory calculations were utilized to allow for a detailed assignment of the experimental spectra. The studied complexes have a range of different coordination spheres, which allows the influence of the ligand donor/acceptor properties on the spectra to be assessed. Similarly, the contributions of the site symmetry and the oxidation state of the metal were analyzed. Because the 4d-to-2p emission lines are dipole-allowed, the spectral features are intense. Furthermore, in contrast with K- or L-edge X-ray absorption of 4d transition metals, which probe the unoccupied levels, the observed 4p-to-2p XES arises from electrons in filled-ligand- and filled-metal-based orbitals, thus providing simultaneous access to the ligand and metal contributions to bonding. As such, 4d-to-2p XES should be a promising tool for the study of a wide range of 4d transition-metal compounds

Modern X-ray spectroscopy: XAS and XES in the laboratory

X-ray spectroscopy is an important tool for scientific analysis. While the earliest demonstration experiments were realised in the laboratory, with the advent of synchrotron light sources most of the experiments shifted to large scale synchrotron facilities. In the recent past there is an increased interest to perform X-ray experiments also with in-house laboratory sources, to simplify access to X-ray absorption and X-ray emission spectroscopy, in particular for routine measurements. Here we summarise the recent developments and comment on the most representative example experiments in the field of in-house laboratory X-ray spectroscopy. We first give an introduction and some historic background on X-ray spectroscopy. This is followed by an overview of the detection techniques used for X-ray absorption and X-ray emission measurements. A short paragraph also puts related high energy resolution and resonant techniques into context, though they are not yet feasible in the laboratory. At the end of this section the opportunities using wavelength dispersive X-ray spectroscopy in the laboratory are discussed. Then we summarise the relevant details of the recent experimental laboratory setups split into two separate sections, one for the recent von Hamos setups, and one for the recent Johann/Johansson type setups. Following that, focussing on chemistry and catalysis, we then summarise some of the notable X-ray absorption and X-ray emission experiments and the results accomplished with in-house setups. In a third part we then discuss some applications of laboratory X-ray spectroscopy with a particular focus on chemistry and catalysis.ISSN:0010-854

Shell-dependent core-level chemical shifts observed in free xenon clusters

Photoelectron and Auger electron spectra following Xe-3d and Xe-4d ionization of free xenon clusters have been measured using synchrotron radiation. The atom-to-surface and atom-to-bulk binding energy shifts found in the Xe-3d and the subsequent M5N4,5N4,5 Auger decay are about 15% larger than those observed in the Xe-4d and N4,5O2,3O2,3 measurements. This experimental result is also considered theoretically

The spin and orbital contributions to the total magnetic moments of free Fe, Co, and Ni clusters

We present size dependent spin and orbital magnetic moments of cobalt (Co$_{n}$$^{+}$, 8 ≤ n ≤ 22), iron (Fe$_{n}$$^{+}$, 7 ≤ n ≤ 17), and nickel cluster (Ni$_{n}$$^{+}$, 7 ≤ n ≤ 17) cations as obtained by X-ray magnetic circular dichroism (XMCD) spectroscopy of isolated clusters in the gas phase. The spin and orbital magnetic moments range between the corresponding atomic and bulk values in all three cases. We compare our findings to previous XMCD data, Stern-Gerlach data, and computational results. We discuss the application of scaling laws to the size dependent evolution of the spin and orbital magnetic moments per atom in the clusters. We find a spin scaling law “per cluster diameter,” ~n$^{−1/3}$, that interpolates between known atomic and bulk values. In remarkable contrast, the orbital moments do likewise only if the atomic asymptote is exempt. A concept of “primary” and “secondary” (induced) orbital moments is invoked for interpretation

X-ray parabolic lenses made from glassy carbon by means of laser

Parabolic planar compound refractive lenses (CRLs) made from glassy carbon by means of laser ablation are presented. They have radii of curvatures of 5 and 200 mu m and geometric apertures of 40 and 900 mu m, respectively. The numbers of biconcave elements in the CRLs were 4, 7, and 200. The planar lenses allow formation of a linear focus of length comparable with the depths of their profiles. Usage of two CRLs in a crossed geometry provides formation of two-dimensional focus. The lenses were tested at the European Synchrotron Radiation Facility at the bending magnet beam line BM-5. The minimum experimental size of the focus has been achieved as 1.4 mu m

Localized versus delocalized excitations just above the 3d threshold in krypton clusters studied by Auger electron spectroscopy

We present Auger spectroscopy studies of large krypton clusters excited by soft x-ray photons with energies on and just above the 3d(5/2) ionization threshold. The deexcitation spectra contain new features as compared to the spectra measured both below and far above threshold. Possible origins of these extra features, which stay at constant kinetic energies, are discussed: (1) normal Auger process with a postcollision interaction induced energy shift, (2) recapture of photoelectrons into high Rydberg orbitals after Auger decay, and (3) excitation into the conduction band (or "internal" ionization) followed by Auger decay. The first two schemes are ruled out, hence internal ionization remains the most probable explanation. (C) 2007 American Institute of Physics