Ionization potentials and geometrical structure of pure and oxygenated barium clusters

In this article, we present results obtained on structures of small bare and oxygenated barium clusters produced by the laser vaporization technique. Contrary to the very weak Ba—Ba binding (0.202 eV), the Ba—O binding is rather strong (5.8 eV). As a consequence, extremely small amounts of oxygen in the cluster source are sufficient to induce the nucleation of oxygenated barium clusters. Surprisingly, at least for substoechiometric systems, Ba_nO_m clusters exhibit the same icosahedral structure as bare clusters do. Mass spectra seem to indicate that replacing a barium atom with a strongly polar BaO molecule does not affect the geometrical structure of the cluster. This aspect is more easily understandable if we assume that the oxygen atom takes place inside the structure of the Ba_n cluster without significant distortions. Ab-initio calculations have been undertaken in order to give a satisfactory account of this hypothesis.     

Residual entropy of glasses and their relation with the crystallization behaviour

For the alloy of eutectic composition in the quasibinary GeSe₂-Sb₂Se₃ system the heat capacities of the glass, undercooled and stable liquid and crystalline phases have been measured using differential scanning calorimetry. Enthalpy, entropy and Gibbs free energy differences of vitreous and crystalline forms have been deduced for this alloy. The kinetic parameters of crystallization for glasses of nearby composition have been obtained by continuous heating experiments. The effective activation energy obtained has a value that accounts for the activation energy for nucleation calculated using simple nucleation theory formulae.

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Zusammenfassung Die Wärmekapazitäten von Glas, unterkühlter und stabiler Flüssigkeit und kristallinen Phasen von Mischungen der eutektischen Zusammensetzung des quasibinären Systems GeSe₂-Sb₂Se₃ werden mittels DSC gemessen. Aus den Ergebnissen werden Enthalpie, Entropie und freie Enthalpie der glasartigen und kristallinen Formen dieser Mischung abgeleitet. Die kinetischen Parameter der Kristallisation von Gläsern benachbarter Zusammensetzungen wurden durch temperaturprogrammierte Untersuchungen ermittelt. Die erhaltenen effektiven Aktivierungsenergien entsprechen dem für die Keimbildung nach einfachen theoretischen Formeln berechneten Wert.

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, , GeSe₂-Sb₂Se₃. , . . , .

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This research was supported by the Comisión Asesora de Investigatión Cientifica y Técnica (CAICYT) project no. 759-84 which is gratefully acknowledged.     

Crystallization kinetic studies: A means to evaluate time-temperature-transformation curves. Application to metallic glasses

It is shown that the study of the kinetics of crystallization of an amorphous alloy may be used to obtain the correct form of the low temperature part of the time-temperature-transformation (T-T-T) curves. A unified review of the current kinetics of crystallization studies is presented and the general kinetic equation which gives the reaction rate as a function of temperature and crystalline fraction is shown to contain information related to theT-T-T-curves. Finally examples of application to two metallic glasses, Nd₃Fe₇₇B₂₀ and Fe_67.5Co₁₅Nb_1.5B₁₆, obtained by rapid solidification techniques are presented. The comparison between theory and experiment is satisfactory.

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Zusammenfassung Es wird gezeigt, daß die Untersuchung der Kristallisationskinetik von amorphen Legierungen genutzt werden kann, die korrekte Form des Niedertemperaturbereiches der Zeit-Temperatur-Transformation (T-T-T) Kurven zu erhalten. Es wird ein einheitlicher Überblick über die jüngsten Untersuchungen von Kristallisationskinetiken gegeben und an der allgemeinen Gleichung der Reaktionsgeschwindigkeit als eine Funktion von Temperatur und Kristallanteil wird gezeigt, daß sie Informationen bezüglich der T-T-T-Kurven beinhaltet. Letztlich wird eine Anwendung an zwei, durch schnelles Erstarren gewonnenen metallischen Gläsern Nd₃Fe₇₇B₂₀ und Fe_67.5Co₁₅Nb_1.5B₁₆ dargelegt. Zwischen Theorie und Praxis konnte eine ausreichende Übereinstimmung festgestellt werden.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday

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This work was supported by the Comision Interdepartamental de Cienca y Tecnologia, CICYT (project No. MAT88-0439) which are acknowledged.     

FAIMS-MS-IR spectroscopy workflow: a multidimensional platform for the analysis of molecular isoforms

An original workflow allowing inline FAIMS separation, electrospray ionization, mass analysis and ion spectroscopy (IRMPD: InfraRed Multiple Photon Dissociation) is presented for multidimensional molecular analysis. This new instrument consists of an ultraFAIMS (Owlstone) device interfaced to a linear ion trap (LTQ XL Thermo Scientific) which was modified for IRMPD spectroscopy. Two modes of operation are demonstrated on an isomeric mixture of paracetamol and 2-phenylglycine. In the first mode a FAIMS (high-Field Asymmetric waveform Ion Mobility Spectrometry) separation of the isomers is performed with a static compensation field for mass- and isomer- selective ion spectroscopy. In the second mode, the compensation field is scanned while the ions are irradiated at a fixed wavenumber. The advantages of this workflow as compared to traditional FAIMS-MS and IRMPD spectroscopy are described. The potential of the two modes for molecular spectroscopy and analytical applications, in particular the new “omics” are discussed.     

Photoionization microscopy

We present the first experimental results of a technique called photoionization microscopy. Photoelectrons ejected in threshold photoionization of Xe are detected in a velocity map imaging apparatus, and interferences between various trajectories by which the electron moves from the atom to the detector are observed. The structure of the interference pattern, which contains the transverse component of the electronic wave function, evolves smoothly with the excess energy above the saddle point. The main observed features are interpreted within the framework of the semiclassical approximation.     

Second mode transition in microstructured optical fibers: determination of the critical geometrical parameter and study of the matrix refractive index and effects of cladding size

We carried out a numerical study of the second mode transition in finite-sized, microstructured optical fibers (MOFs) for several values of the matrix refractive index. We determined a unique critical geometrical parameter for the second mode cutoff that is valid for all the matrix refractive indices studied. Finite size effects and extrapolated results for infinite structures are described. Using scaling laws, we provide a generalized phase diagram for solid-core MOFs that is valid for all refractive indices, including those of the promising chalcogenide MOFs.     

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