Dynamical effects in the vibrationally resolved C 2s-1 photoionization cross section ratios of Methane

The vibrationally resolved C 2s photoionization cross-section of methane was investigated both theoretically and experimentally. When compared to that of C 1s photoionization, a rather different pattern has been observed, suggesting a strong interplay between the electron diffraction and interference effects

Vibration dependent branching and photoelectron angular distributions observed across the Cooper minimum region of bromobenzene

Vibrational state-resolved photoelectron anisotropy parameters, beta, for the ~X 2B1, ~B 2B2, and ~C2B1 state ionizations of bromobenzene have been recorded at photon energies ranging from 20.5 to 94 eV, so spanning the region of the expected bromine Cooper minimum (CM). The ~X state displays no CM and its beta value is also independent of vibrational level, in accord with the Franck-Condon Approximation. The ~B and ~ C state beta values display the CM to differing degrees, but both show a vibrational dependence that extends well below the obvious CM dip. Calculations are presented that replicate these observations of Franck-Condon Approximation breakdown spanning an extended photon energy range. This is the first demonstration of such wide-ranging breakdown detected in the beta anisotropy parameter in the absence of any resonance. Measured and calculated vibrational branching ratios for these states are also presented. Although the ~B state branching ratios remain constant, in accord with Franck-Condon expectations, the ~X and (especially) the ~C state ratios display weak, quasi-linear variations across the studied range of photon energy, but with no apparent correlation with the CM position

Proton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries

Hydrogen bonding leads to the formation of strong, extended intermolecular networks in molecular liquids such as water. However, it is less well-known how robust the network is to environments in which surface formation or confinement effects become prominent, such as in clusters or droplets. Such systems provide a useful way to probe the robustness of the network, since the degree of confinement can be tuned by altering the cluster size, changing both the surface-to-volume ratio and the radius of curvature. To explore the formation of hydrogen bond networks in confined geometries, here we present O 1s Auger spectra of small and large clusters of water, methanol, and dimethyl ether, as well as their deuterated equivalents. The Auger spectra of the clusters and the corresponding macroscopic liquids are compared and evaluated for an isotope effect, which is due to proton dynamics within the lifetime of the core hole (proton-transfer-mediated charge-separation, PTM-CS), and can be linked to the formation of a hydrogen bond network in the system. An isotope effect is observed in water and methanol but not for dimethyl ether, which cannot donate a hydrogen bond at its oxygen site. The isotope effect, and therefore the strength of the hydrogen bond network, is more pronounced in water than in methanol. Its value depends on the average size of the cluster, indicating that confinement effects change proton dynamics in the core ionised excited state

Lignans in Knotwood of Norway Spruce : Localisation with Soft X-ray Microscopy and Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy

Lignans are bioactive compounds that are especially abundant in the Norway spruce (Picea abiesL. Karst.) knotwood. By combining a variety of chromatographic, spectroscopic and imaging techniques, we were able to quantify, qualify and localise the easily extractable lignans in the xylem tissue. The knotwood samples contained 15 different lignans according to the gas chromatography-mass spectrometry analysis. They comprised 16% of the knotwood dry weight and 82% of the acetone extract. The main lignans were found to be hydroxymatairesinols HMR1 and HMR2. Cryosectioned and resin-embedded ultrathin sections of the knotwood were analysed with scanning transmission X-ray microscopy (STXM). Cryosectioning was found to retain only lignan residues inside the cell lumina. In the resin-embedded samples, lignan was interpreted to be unevenly distributed inside the cell lumina, and partially confined in deposits which were either readily present in the lumina or formed when OsO(4)used in staining reacted with the lignans. Furthermore, the multi-technique characterisation enabled us to obtain information on the chemical composition of the structural components of knotwood. A simple spectral analysis of the STXM data gave consistent results with the gas chromatographic methods about the relative amounts of cell wall components (lignin and polysaccharides). The STXM analysis also indicated that a torus of a bordered pit contained aromatic compounds, possibly lignin.Peer reviewe

Unraveling compensation between electron transfer and strain in Ni-Ag-MoS2 photocatalyst

Despite the boom in catalytic response via constructing interfaces, understanding interfaces’ interaction in heterostructures is still a paradox. In this work, the interaction of Ni with MoS2 in Ni-Ag-MoS2 heterostructure are unveiled through synchrotron X-PEEM and what\u27s more, the missing interaction mechanism at the Ag-MoS2 interface is probed via Raman mapping. The observed competition between the downshift of the E2g1 and A1g modes due to charge carrier injection and the upshift of the E2g1 and A1g modes due to compressive strain during reverse laser power experiment is assigned to the non-uniform growth of Ag nanoparticles, their intimate contact with MoS2, and Ag intercalated layered MoS2. The substantial improvement of the H2 yield of the Ni-Ag-MoS2 (∼55 μmol h−1 g−1) over the pristine MoS2 and the binary Ag-MoS2 evidence successful bonding of Ni, Ag and MoS2. This study highlights the importance of considering both electronic coupling and strain to optically tune electromechanical properties of MoS2

X-ray induced fragmentation of size-selected salt cluster-ions stored in an ion trap

Peer reviewe

Chemical mapping of Norway spruce lignans in knotwood cells

201

Synchrotron‐Radiation‐Based Soft X‐ray Electron Spectroscopies Applied to Structural and Chemical Characterization of Isolated Species, from Molecules to Nano‐objects

International audienceWith its extended tunability from the IR to hard X-rays and the exceptional spectral brightness offered by the third generation storage rings, synchrotron radiation (SR) has become an invaluable investigation tool. Major methodological developments have been recently undertaken, first applied to simple systems, isolated atoms and molecules - that can be often modeled ab initio - and then extended to the investigation of more and more complex species, up to the soft and hard condensed matter. Here, we present some of the most recent achievements in SR-based soft X-ray electron spectroscopy applied to the structural characterization of isolated species of increasing complexity from molecules to clusters and nanoparticles. Special attention is devoted to very high-resolution studies of free molecules revealing physical phenomena such as electron diffraction and interference effects, as well as detailed information about the potential energy surfaces. Beyond this, we will see how technical progress of SR-based soft X-ray spectroscopy opens new routes to structural studies on freestanding nanosystems. These achievements have only become possible using the new experimental opportunities offered by the most advanced SR facilities

Electron spectroscopy using ultra brilliant synchrotron X-ray sources

The development of photoelectron spectroscopy since the early days of the technique is discussed. The focus is on the interaction between instrumental development and scientific achievements. In particular the opportunities provided by the increasingly brilliant synchrotron radiation sources are discussed. The contribution is focused on core level studies. The recent development is demonstrated by using selected examples obtained at today's most advanced synchrotron radiation facilities. The spectral resolution and intensity that can be reached at these facilities reveal new effects and provide detailed information on the investigated systems. The examples are mainly taken from studies of atoms and molecules where different effects can be most accurately identified and separated.UBj