Experimental study of photoionization of ozone in the 12 to 21 eV region

The total and partial ion yield of ozone using time-of-flight is presented. The measurements were done using multicoincidence between a photoelectron and a photoion (PEPICO). Comparison with the photoelectron spectrum and previous measurements using other techniques allowed the assignment of most broad features in the spectra. Kinetic energy released is obtained for O+ and O-2(+) ions. A discussion about the dissociation channels is included. (C) 2001 American Institute of Physics.115115041504

Plasmon single- and multi-quantum excitation in free metal clusters as seen by photoelectron spectroscopy.

Plasmons are investigated in free nanoscale Na, Mg, and K metal clusters using synchrotron radiation-based x-ray photoelectron spectroscopy. The core levels for which the response from bulk and surface atoms can be resolved are probed over an extended binding energy range to include the plasmon loss features. In all species the features due to fundamental plasmons are identified, and in Na and K also those due to either the first order plasmon overtones or sequential plasmon excitation are observed. These features are discussed in view of earlier results for planar macroscopic samples and free clusters of the same materials

Probing aqueous ions with non-local Auger relaxation

Non-local analogues of Auger decay are increasingly recognized as important relaxation processes in the condensed phase. Here, we explore non-local autoionization, specifically Intermolecular Coulombic Decay (ICD), of a series of aqueous-phase isoelectronic cations following 1s core-level ionization. In particular, we focus on Na+, Mg2+, and Al3+ ions. We unambiguously identify the ICD contribution to the K-edge Auger spectrum. The different strength of the ion-water interactions is manifested by varying intensities of the respective signals: the ICD signal intensity is greatest for the Al3+ case, weaker for Mg2+, and absent for weakly-solvent-bound Na+. With the assistance of ab initio calculations and molecular dynamics simulations, we provide a microscopic understanding of the non-local decay processes. We assign the ICD signals to decay processes ending in two-hole states, delocalized between the central ion and neighbouring water. Importantly, these processes are shown to be highly selective with respect to the promoted water solvent ionization channels. Furthermore, using a core-hole-clock analysis, the associated ICD timescales are estimated to be around 76 fs for Mg2+ and 34 fs for Al3+. Building on these results, we argue that Auger and ICD spectroscopy represents a unique tool for the exploration of intra- and inter-molecular structure in the liquid phase, simultaneously providing both structural and electronic information

Photoelectron diffraction: from phenomenological demonstration to practical tool

The potential of photoelectron diffraction—exploiting the coherent interference of directly-emitted and elastically scattered components of the photoelectron wavefield emitted from a core level of a surface atom to obtain structural information—was first appreciated in the 1970s. The first demonstrations of the effect were published towards the end of that decade, but the method has now entered the mainstream armoury of surface structure determination. This short review has two objectives: First, to outline the way that the idea emerged and the way this evolved in my own collaboration with Neville Smith and his colleagues at Bell Labs in the early years: Second, to provide some insight into the current state-of-the art in application of (scanned-energy mode) photoelectron diffraction to address two key issue in quantitative surface structure determination, namely, complexity and precision. In this regard a particularly powerful aspect of photoelectron diffraction is its elemental and chemical-state specificity

Tuning the oxidation degree in sub-10 nm silver-oxide nanoparticles: From Ag2O monoxide to AgOx(x > 1) superoxide

A preparation method for silver-oxide containing nanoparticles is described. The suggested approach allows varying the oxidation degree from monoxide to an oxygen-rich state resembling superoxide The method is based on magnetron reactive sputtering and vapour aggregation, and utilizes silver-oxygen interaction in the vapour phase - prior to the nanoparticle aggregation from the vapour. Synchrotron-based photoelectron spectroscopy - a local probing method with high chemical sensitivity - allows 'on-the-fly' analysis of the composition and oxidation degree in nanoparticles, before any deposition of the particles. Preparation and properties of oxygen-rich nanoparticles are discussed in connection to the catalytic processing of economically important hydrocarbons. (C) 2014 Elsevier B.V. All rights reserved

Charge delocalization dynamics of ammonia in different hydrogen bonding environments: free clusters and in liquid water solution

Valence and core level photoelectron spectra and Auger electron spectra of ammonia in pure clusters have been measured. The Auger electron spectra of gas-phase ammonia, pure ammonia clusters and ammonia in aqueous solution are compared and interpreted via ab initio calculations of the Auger spectrum of the ammonia monomer and dimer. The calculations reveal that the final two-hole valence states can be delocalized over both ammonia molecules. Features at energies pertaining to delocalized states involving one, or more, hydrogen bonding orbitals can be found in both the ammonia cluster Auger electron spectrum and in that of the liquid solvated molecule. The lower Coulombic repulsion between two delocalized valence final state holes gives higher kinetic energy of the Auger electrons which is also observed in the spectra. This decay path-specific to the condensed phase-is responsible for more than 5% of the total cluster Auger intensity. Moreover, this interpretation is also applicable to the solid phase since the same features have been observed, but not assigned, in the Auger spectrum of solid ammonia

Photon Energy Dependent Valence Band Response of Metallic Nanoparticles

We show that the valence band response to photon impact in metallic nanoparticles is highly energy dependent. This is seen as drastic variations of cross sections in valence photoionization of free and initially charge-neutral nanosized metal clusters. The effect is demonstrated in a combined experimental and theoretical study of Rb clusters. The experimental findings are interpreted theoretically using a jellium model and superatom description. The variations are attributed to the changing overlap with the photon energy between the wave functions of diffuse delocalized valence electrons and continuum electrons producing a series of minima in the cross section

The influence of the sigma resonance on the Auger decay of core-ionized molecular nitrogen

Auger spectra from the decay of core-ionized N-2 have been studied as a function of the exciting photon energy. Discrete features appear in the Auger spectrum when the photon energy is tuned to the shape-resonance region at 420 eV. The Auger spectra for two final dicationic states are studied; simulations of the contributions from the decay of the gerade and ungerade core-hole states are made based on a Franck-Condon picture including life time vibrational interference. We are able to reproduce the vibrational. ne structure in the Auger spectrum using a model where the coherent sum of the decay channels from the vibrationally-excited states are treated separately for the gerade and ungerade states

The geometric structure of pure SF6 and mixed Ar/SF6 clusters investigated by core level photoelectron spectroscopy

The S 2p core level photoelectron spectra of Sulphurhexafluoride Clusters have been investigated together with heterogeneous Ar/SF6 clusters, created by doping Ar host clusters (with a mean size of 3600 atoms) with the molecule. Surface and bulk features are resolved both in the argon 2p and the sulphur 2p core level photoelectron spectra. For the latter level such features were only observed in the pure cluster case; a single feature characterizes the S 2p core level spectra of SF6 doped argon clusters. From the chemical shifts, investigated with respect to SF6 doping pressure. It can be concluded that the host clusters get smaller with increasing doping pressures and that the SF6 molecules predominantly stay below the cluster surface, whereas the Argon core stays intact. We have neither observed features corresponding to SF6 on the cluster Surface, nor features corresponding to molecules deep inside the bulk in any of the spectra from the pick-up experiments. (C) 2008 Elsevier B.V. All rights reserved

Increased Propensity of I-aq(-) for the Water Surface in Non-neutral Solutions: Implications for the Interfacial Behavior of H3Oaq+ and OHaq-

By a combination of surface-sensitive photoelectron spectroscopy and molecular dynamics simulations, we characterize the surface propensity of the iodide anion in aqueous solutions at acidic, neutral, and basic conditions (pH = 1, 6.8 and 13). In both experiments and simulations, an increased surface concentration of I- is found in non-neutral solutions. We interpret these findings in terms of I- surface coadsorption with hydronium at low pH and "salting out" of iodide by hydroxide from the bulk solution to the surface at high pH. The present study is thus in accord with the picture of a weak surface adsorption of hydronium and surface depletion of hydroxide, being in sharp contradiction with the interpretation of electrophoretic and titration measurements in terms of strong surface enrichment of OH-