• ANALYTICAL APPLICATIONS OF PARTICLE INDUCED X-RAY EMISSION (PIXE) SPECTROSCOPY

      Fernando, Quintus; Kirchner, Stephen John (The University of Arizona., 1981)
      Quantitative multielemental analysis using Particle Induced X-ray Emission (PIXE) using 1 and 2 MeV proton bombardment on thin targets has been achieved. The method is based on the calculation of atomic ratios from experimentally determined relative x-ray efficiency curves. Sample preparation techniques involving digestion and homogenous deposition of samples and standards with a minimum of contamination have been investigated. The accuracy of the method has been evaluated using five standard reference materials obtained from the National Bureau of Standards. The elimination of bremsstrahlung associated with the charging effect of non-conducting samples in PIXE analysis has been accomplished using thin carbon foils in the beam path. Applications of the PIXE technique to studies on deep-sea ferromanganese nodules were performed. The utility of PIXE in the analysis of noduoles and in the following of the distribution of a large number of elements through the various stages of a processing scheme were demonstrated.
    • CHARACTERISTIC AND NON-CHARACTERISTIC X-RAYS FROM ION-ATOM COLLISIONS

      Oona, Henn, 1939- (The University of Arizona., 1974)
    • THE ELECTRONIC STRUCTURE OF ORGANOMETALLIC CARBONYL, NITROSYL, THIONITROSYL, AND CYANIDE COMPLEXES BY GAS PHASE X-RAY AND ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY.

      Lichtenberger, Dennis; HUBBARD, JOHN LEE. (The University of Arizona., 1982)
      Transition metal-ligand interactions in several groups of closely related organometallic complexes are discussed from the results of both valence and core photoelectron experiments. Particular attention is given to the novel experimental aspects, including a charged particle oscillator He II source, sample introduction and containment, and data collection and spectral analysis procedures not normally associated with gas phase photo-electron spectroscopy. The application of the ionization experiments begins with a reassessment of the bonding in the group VIb metal hexacarbonyls. He I ionization data of unprecedented quality for the predominantly metal d t₂g level of Cr(CO)₆ and W(CO)₆ reveals for the first time the presence of metal-carbon vibrational fine structure. These positive ion M-C stretching frequencies are significantly reduced from neutral ground state values, giving direct evidence of the pi back-bonding nature of the t₂g level. The next chapter focuses on the comparison of the metal-nitrosyl interactions in the trans-X-W(CO)₄NO complexes to the isoelectronic/isostructural metal-carbonyl interactions in the X-Re(CO)₅ complexes (X = Cl,Br,I). A further comparison of carbonyl and nitrosyl bonding, as well as the first photoelectron assessment of metal-thionitrosyl bonding, is addressed in the next chapter by comparing the valence and core ionization data for CpCr(CO)₂NO and CpCr(CO)₂NS (Sp = η⁵-C₅H₅) to the data reported earlier for CpMn(CO)₃ and CpMn(CO)₂CS. The final chapter of the dissertation compares the electronic structure of the CpFe(CO)₂X complexes to their CpCr(NO)₂X analogs (X = Cl,Br,I,CH₃,CN). The essence of this work fully contrasts the Fe(CO)₂ and Cr(NO)₂ functional groups.
    • X-RAY EMISSION FROM LASER-HEATED SPHERICAL PLASMAS.

      MOSTACCI, DOMIZIANO VALERIO. (The University of Arizona., 1985)
      A model has been developed for calculating x-ray line emission from spherical plasmas. The main features of this method are: (1) Plasma parameters are obtained from a one-dimensional Lagrangian hydrodynamics and heat flow code. (2) Multi-frequency groups: the line structure can be reproduced with the desired accuracy by adjusting the number of frequency groups. (3) Self consistent, time dependent excited level populations and radiation fluxes: the code starts with coronal populations, calculates the ensuing radiation flux and then recalculates the populations and so on, iterating until convergence is reached. (4) Goemetrical groups of rays groups by spherical impact parameters. (5) Line broadening due to ionic thermal agitation and Doppler shift due to the net plasma flow velocity. Inclusion of the flow velocity shift would be different without the multi-frequency group treatment. The method has been applied to an aluminum target, and the results are in good agreement with previous experimental work. The total energy, summed over all lines, as well as the line intensity ratios (which are a sensitive measure of agreement with experiment) were predicted with good accuracy. The pictures that would be seen by a pinhole camera are also calculated by the code.