Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (M. Phil.)--Hong Kong University of Science and Technology, 2002. / Includes bibliographical references. Also available in electronic version. Access restricted to campus users.

Thesis (Ph. D.)--Brigham Young University. Dept. of Chemistry and Biochemistry, 2004. / Includes bibliographical references.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

A high resolution speedy delivery time domain reflectometer (SD/TDR) has been developed in the Electrical Engineering department at The University of Texas at Austin. The SD/TDR uses a novel non-sinusoidal signal that does not undergo dispersion during transmission in a lossy media. SD/TDR is used to estimate the length and detect the location of faults in the transmission lines. Time of flight (TOF) is one of the critical parameters of SD/TDR and a function of several temperature dependent factors. Given the TOF and length of a transmission line, signal delay can be computed. This research presents an empirical study of the effect of temperature on the TOF in a plenum grade coaxial cable for temperatures ranging from -3 °C to 60 °C. We also study the effect of temperature on characteristic impedance of the coaxial cable. Finally, a SD double exponential waveform is used to estimate TOF for calibrated short and open terminations. / text

The application of inductively coupled plasma time-of-flight mass spectrometers (ICP-TOFMS) coupled to electrothermal vaporization (ETV) presents several unique analytical opportunities for isotopic analysis. This dissertation explores several subjects that utilize these characteristics in specific analytical applications. The viability of using the thermal programming abilities of the ETV in order to separate Rb and Sr is explored. These elements are isobaric at m/z 87, and must normally be separated prior to analysis for isotopic studies. Their disparate thermal properties allow them to be separated in time by the ETV allowing for simpler, faster isotope ratio analysis with less opportunity for contamination. A test case using standard potassium feldspar is found to produce moderately accurate and precise results. TOF instruments are of interest for isotope ratio analysis due to inherent isotope ratio precision. However, it has been observed that when operated in the analog data collection mode the isotope ratios observed possess a previously uncharacterized inaccuracy. This bias is rooted in variable detection efficiency of arriving ions, which can be corrected for with an algorithm described within. A method of determining the effective detector efficiency as a function of signal is presented, as well as an evaluation of the effectiveness of ratio correction. The use of ETV with TOF for isotope dilution analysis is explored. Correction of transient signals for efficiency effects is discussed, as well as the viability of using the autosampler for mixing of the solution and spike. A final study presents explores the combination of the ETV and TOF for analysis of a large number of elements from a brief transient signal. A library of peptide covered beads is analyzed for binding capacity to a variety of metals. Solutions containing metals stripped from the beads are analyzed to determine the binding capacity and specificity of the peptide sequence. The beads themselves are also analyzed for metal content using the ETV as an indicator of the efficiency of metal stripping off of the beads. / text

Polyyne molecules were produced as a result of the femtosecond laser irradiation of liquid acetone (CH3)2CO and alkane molecules hexane C6H14 and octane C8H18 using 800 nm, 100 fs duration pulses. These polyynes have been detected as a Raman band in irradiated liquid from 1800 to 2200 cm−1. Polyyne molecules generally detected as a Raman band in SERS experiment are C8H2, C10H2, C12H2 and C14H2. Two well established experimental techniques, time of flight mass spectrometry and surface enhanced Raman spectrometry were used to identify positively polyyne formation as a result of femtosecond laser irradiation of acetone and alkane liquids. Small polyynes C2H2, C4H2, and C6H2 were positively detected in the time of flight mass spectrometer TFMS, while longer polyynes from C6H2, C8H2, C10H2, C12H2 and C14H2 were detected by surface enhanced Raman spectroscopy SERS. Intensity capping occurs in a liquid due to filamentation, and the resulting intensity in a liquid is s 1013 W/cm2 during irradiation. This results in main process of ionization in the larger part of the laser focus as multiphoton ionization MPI. Focal volume increase in a liquid provides a larger volume where ions C+, C+2 and C2+are produced to initiate chemical reactions outside the laser focus. The current work established positively, that the longer polyyne formation does not occur by dehydrogenation of alkane molecules by only breaking the C-H bonds as was previously anticipated. It is proposed in this work that lengthening of polyyne chains occurs due to addition reaction of species of C+, C+2 and C2+ to double bonded species themselves produced as a result of the breaking down of the parent molecules in the laser focus. The carbon addition reactions occur outside the laser focus due to the close proximity of molecules in the liquid phase.

No description available.

Mass spectrometers are analytical instruments that convert neutral atoms and molecules into gaseous ions and separate those ions according to the ratio of their mass to charge, m/z. The measurement is reported as a mass spectrum: a plot of relative intensity vs. m/z that can be used to deduce the chemical structure and composition of materials and compounds. Initially, the use of mass spectrometers was restricted to the analysis of volatile compounds. Recent advances in the development of ionisation techniques to produce intact molecules directly from samples in the liquid or solid phase, has extended the powerful use of mass spectrometry to compounds of increasingly higher molecular mass. The aim of this study was twofold: develop diagnostic techniques for the in-situ measurement of isotope ratios in laser isotope separation experiments; and to correlate it with the measured isotope ratios on the collected product. The outcome is a thesis that can be divided into two distinct fields of application: Firstly; the Atomic Vapour Laser Isotope Separation (AVLIS) of lithium, and secondly the Molecular Laser Isotope Separation (MLIS) of uranium, In both AVLIS and MLIS pulsed laser systems were used to ionise and/or dissociate atomic or molecular beams. The pulsed nature of the lasers is ideally suited to in-situ time-of-flight detection of the produced ions. Different types of inter-changeable ion sources are common to the same TOF mass spectrometer. Each of these sources is selected according to its application. For instance, applications vary from photo- and multiphoton ionisation (laser ionisation) to surface analysis (laser desorption or particle bombardment) to chromatography (electron impact ionisation). Four different source configurations were considered in this study: (i) Atomic Laser Isotope Separation (AVLIS) of lithium; (ii) Multiphoton Ionisation (MPl) of UF6 gas; (iii) Non-resonant ionisation during Laser Desorption (LDI) of solids; and (iv) Matrix-Assisted Laser Desorption (MALD) of biopolymers. The design of each of these sources will be discussed in detail in chapters to follow. Bulk analysis of harvested laser-produced products needs to be in correlation with in-situ analysis. Three different characterisation methods were used in this study: (i) Laser Desorption Time-of-Flight Mass Spectrometry (LD-TOF-MS) (ii) Quadrupole-based Secondary Ion Mass Spectrometry (SIMS); and (iii) TOF-MS-based Secondary Ion Mass Spectrometry (TOF-SIMS). Chapter I describes the principles of time-of-flight mass spectrometry, design parameters, as well as the instrumentation that were designed and constructed for the purposes of this study. Chapter II describes the principles of Secondary Ion Mass Spectrometry (SIMS). In particular, research done on the establishment of tools to the non-expert user of SIMS to select analyses conditions, is described. Chapter III reports on the application of TOF-MS and SIMS during the AVLIS of lithium. Chapter IV reports on the application of the different combinations of TOF-MS, LD-TOF-MS, SIMS, and TOF-SIMS during the MLIS of uranium. / Thesis (Ph.D.)-University of Natal, Durban, 1999.

This thesis is based on experimental results from measurements on methyl halides at a photon energy corresponding to the He IIβ emission line. Double ionization processes involving the valence electrons of the molecules CH3F, CH3Cl and CH3I are studied by means of a magnetic bottle TOF-PEPECO spectrometer. Resulting double ionization data of these molecules suggest that mainly direct double photoionization is observed as a continuous energy sharing between the ejected electron pairs. As a mean to further understand the double ionization processes, a "rule of thumb", for double ionization in molecules, is applied to the data presented in the double ionization spectra. This is done in order to quantify the effective distance between the two vacancies created in the dications. It is found that the distance between the vacancies may be related to the bond distance between the carbon and halogen atoms. Further investigations call for quantum chemical calculations to scrutinize this hypothesis. / Det här examensarbetet är baserat på experimentella fotojonisations studier av metyl halider vid en fotonenergi motsvarande He IIβ emissionslinjen. Valenselektronerna i dubbeljonisations processerna för CH3F, CH3Cl och CH3I har studerats under användning av en så-kallad magnetisk flask TOF-PEPECO spektrometer. Resultaten av dessa mätningar visar att mestadels direkt dubbeljonisation processer före- kommer, där elektronerna delar kontinuerligt på energin som friges vid jonisationen. Den dubbla jonisa- tions processen är ytterligare studerad genom att tillämpa en tumregel för dubbeljonisation i molekyler, vilket ger en indikation av hur stort avståndet är mellan de två vakanserna som skapades när molekylerna joniserade. Resultaten från tumregeln visar att avståndet mellan vakanserna kan vara relaterade till bind- ningsavståndet mellan kol-atomen och halogen-atomen, i respektive metyl halogen. För att ytterligare bekräfta dubbeljonisations processerna i dessa molekyler, krävs kvantmekaniska beräkningar.