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Pulsed laser ablation in liquid (PLAL) is a powerful method for producing nanoparticle colloids with a long-term stability despite the absence of stabilizing organic agents. The colloid stability involves different reactivities and chemical equilibria with complex ionic-specific effects at the nanoparticle/solvent interface which must be strongly influenced by their chemical composition. In this work, the surface composition of PLAL-produced gold nanoparticles in alkaline and saline (NaBr) water is investigated by X-ray photoelectron spectroscopy on free-flying nanoparticles, exempt from any substrate or radiation damage artifact. The Au 4f photoelectron spectra with a depth profiling investigation are used to evaluate the degree of nanoparticle surface oxidation. In alkaline water, the results preclude any surface oxidation contrary to the case of nanoparticles produced in NaBr solution. In addition, the analysis of Br 3d core-level photoelectron spectra agrees with a clear signature of Br on the nanoparticle surface, which is confirmed by a specific valence band feature. This experimental study is supported by DFT calculations, evaluating the energy balance of halide adsorption on different configurations of gold surfaces including oxidation or adsorbed salts.

Nested sampling is an efficient algorithm for the calculation of the Bayesian evidence and posterior parameter probability distributions. It is based on the step-by-step exploration of the parameter space by Monte Carlo sampling with a series of values sets called live points that evolve towards the region of interest, i.e. where the likelihood function is maximal. In presence of several local likelihood maxima, the algorithm converges with difficulty. Some systematic errors can also be introduced by unexplored parameter volume regions. In order to avoid this, different methods are proposed in the literature for an efficient search of new live points, even in presence of local maxima. Here we present a new solution based on the mean shift cluster recognition method implemented in a random walk search algorithm. The clustering recognition is integrated within the Bayesian analysis program NestedFit. It is tested with the analysis of some difficult cases. Compared to the analysis results without cluster recognition, the computation time is considerably reduced. At the same time, the entire parameter space is efficiently explored, which translates into a smaller uncertainty of the extracted value of the Bayesian evidence.

Nested sampling is an efficient algorithm for the calculation of the Bayesian evidence and posterior parameter probability distributions. It is based on the step-by-step exploration of the parameter space by Monte Carlo sampling with a series of values sets called live points that evolve towards the region of interest, i.e. where the likelihood function is maximal. In presence of several local likelihood maxima, the algorithm converges with difficulty. Some systematic errors can also be introduced by unexplored parameter volume regions. In order to avoid this, different methods are proposed in the literature for an efficient search of new live points, even in presence of local maxima. Here we present a new solution based on the mean shift cluster recognition method implemented in a random walk search algorithm. The clustering recognition is integrated within the Bayesian analysis program NestedFit. It is tested with the analysis of some difficult cases. Compared to the analysis results without cluster recognition, the computation time is considerably reduced. At the same time, the entire parameter space is efficiently explored, which translates into a smaller uncertainty of the extracted value of the Bayesian evidence.

The surface chemistry of gold nanoparticles produced by the pulsed laser ablation in liquids method is investigated by X-ray photoelectron spectroscopy (XPS). The presence of surface oxide expected on these systems is investigated using synchrotron radiation in conditions close to their original state in solvent but free from substrate or solvent effects which could affect the interpretation of spectroscopic observations. For that purpose we performed the experiment on a controlled free-standing nanoparticle beam produced by combination of an atomizer and an aerodynamic lens system. These results are compared with those obtained by the standard situation of deposited nanoparticles on silicon substrate. An accurate analysis based on Bayesian statistics concludes that the existence of oxide in the free-standing conditions cannot be solely confirmed by the recorded core-level 4f spectra. If present, our data indicate an upper limit of 2.15 ± 0.68% of oxide. However, a higher credence to the hypothesis of its existence is brought by the structureless valence profile of the free-standing beam. Moreover, the cross-comparison with the deposited nanoparticles case clearly evidences an important misleading substrate effect. Experiment with free-standing nanoparticles is then demonstrated to be the right way to further investigate oxidation states on Au nanoparticles.

The chemical and geometrical structure of free-standing carbon dots (Cdots) prepared from the pyrolysis of N-hydroxysuccinimide (NHS) have been characterized using X-ray photoelectron spectroscopy (XPS). An aerodynamic lens system was used to generate a sufficient particle density of monodispersed Cdots for XPS studies at the PLEIADES beamline at the SOLEIL synchrotron facility. Varying the X-ray excitation energy between 315 and 755 eV allows probing of the Cdots from the surface toward their core, owing to the kinetic energy dependence of the photoelectron inelastic mean free path. The C 1s, O 1s, and N 1s core-levels were recorded with high-spectral resolution to identify their main chemical components and branching ratios. While high-resolution transmission electron microscopy (HRTEM) reveals a defective graphitic core, the C 1s spectrum evidence two main peaks similar to those measured from the solid NHS. Their relative abundance as a function of the probing depth is strongly related to the chemical composition of the ligand shell that does not vary substantially over the first 3.4 nm. Combining the depth-resolved XPS and HRTEM studies, it was concluded that the Cdots possess a graphitic core surrounded by a relatively homogeneous shell of at least 3.4 nm thickness with a composition similar to that of the solid NHS.

The exploration of the unique properties of stored and cooled beams of highly-charged ions as provided by heavy-ion storage rings has opened novel and fascinating research opportunities in the realm of atomic and nuclear physics research. Since the late 1980s, pioneering work has been performed at the CRYRING at Stockholm (Abrahamsson et al. 1993) and at the Test Storage Ring (TSR) at Heidelberg (Baumann et al. 1988). For the heaviest ions in the highest charge-states, a real quantum jump was achieved in the early 1990s by the commissioning of the Experimental Storage Ring (ESR) at GSI Helmholtzzentrum für Schwerionenforschung (GSI) in Darmstadt (Franzke 1987) where challenging experiments on the electron dynamics in the strong field regime as well as nuclear physics studies on exotic nuclei and at the borderline to atomic physics were performed. Meanwhile also at Lanzhou a heavy-ion storage ring has been taken in operation, exploiting the unique research opportunities in particular for medium-heavy ions and exotic nuclei (Xia et al. 2002).

We present a new evaluation of the negatively charged pion mass based on the simultaneous spec-troscopy of pionic nitrogen and muonic oxygen transitions using a gaseous target composed by a N 2 /O 2 mixture at 1.4 bar. We present the experimental setup and the methods for deriving the pion mass value from the spatial separation from the 5g -- 4 f $\pi$N transition line and the 5g -- 4 f $\mu$O transition line used as reference. Moreover, we discuss the importance to use dilute targets in order to minimize the influence of additional spectral lines from the presence of remaining electrons during the radiative emission. The occurrence of possible satellite lines is investigated via hypothesis testing methods using the Bayes factor.

The population of magnetic sublevels in hydrogen-like uranium ions has been investigated in relativistic ion–atom collisions by observing the subsequent X-ray emission. Using the gas target at the experimental storage ring facility we observed the angular emission of Lyman-α radiation from hydrogen-like uranium ions. The alignment parameter for three different interaction energies was measured and found to agree well with theory. In addition, the use of different gas targets allowed for the electron-impact excitation process to be observed.

The population of magnetic sublevels in hydrogen-like uranium ions has been investigated in relativistic ion-atom collisions by observing the subsequent X-ray emission. Using the gas target at the experimental storage ring facility we observed the angular emission of Lyman-alpha radiation from hydrogen-like uranium ions. The alignment parameter for three different interaction energies was measured and found to agree well with theory. In addition, the use of different gas targets allowed for the electron-impact excitation process to be observed., authorCount :31

We report on time-modulated two-body weak decays observed in the orbital electron capture of hydrogen-like $^{140}$Pr$^{59+}$ and $^{142}$Pm$^{60+}$ ions coasting in an ion storage ring. Using non-destructive single ion, time-resolved Schottky mass spectrometry we found that the expected exponential decay is modulated in time with a modulation period of about 7 seconds for both systems. Tentatively this observation is attributed to the coherent superposition of finite mass eigenstates of the electron neutrinos from the weak decay into a two-body final state., Comment: 12 pages, 5 figures

A twin crystal-spectrometer assembly, operated in the focusing compensated asymmetric Laue geometry has been developed for accurate spectroscopy of fast highly charged heavy ions in the hard-X-ray region. Coupled to the focusing crystal optics is a specially developed two-dimensional position-sensitive X-ray detector which is necessary for retaining spectral resolution also for fast moving sources. We summarize the crystal optics and demonstrate the usefulness of the instrument for spectroscopy of both stationary and fast moving X-ray sources. Results are reported from several tests employing a ¹⁶⁹Yb gamma-ray source and the Lyman radiation of one-electron Pb⁸¹⁺ ions traveling at a velocity corresponding to β ≡ v/c ≈ 0.59. The features of the instrument presented may be useful in many applications where it appears difficult to make the leap from conventional X-ray energy measurements to wavelength-dispersive spectroscopy based on crystal optics.

The line shape of the (3p − 1s) X-ray transition in muonic hydrogen was measured for the first time with a high-resolution crystal spectrometer. The assumption of a statistical population of the hyperfine levels was directly confirmed by experiment, and a measured value for the hyperfine splitting is reported. An X-ray line broadening due to Doppler effect could be clearly identified and attributed to different Coulomb de-excitation transitions which precede the measured radiative transition. The results allow a decisive test of advanced cascade model calculations and establish an alternative and "model free” method to extract the strong-interaction parameters from pionic hydrogen data