More than 40 different molecules have been observed in Interstellar space within the Galaxy. Many of these molecules are seen near hot OB-type stars whose far-ultraviolet emission is intense. Laboratory spectroscopy of such molecules will lead to a better understanding of their astrophysical behaviour, in particular Celestial Masers. This thesis is preoccupied with the spectroscopy of H$_{2}$O, D$_{2}$O, OH, CO, and C$_{2}$H$_{2}$ in the region 1200$\AA$-400$\AA$ and absolute absorption coefficients are derived for CO and C$_{2}$H$_{2}$ using the Thomas-Reiche-Kuhn Sum Rule. A possible Rydberg series of OH was observed, converging to a first ionisation potential of 13.36 eV and a likely inner shell two-electron resonance detected in the ionisation continuum of D$_{2}$O at 415$\AA$. Both a synchrotron and a laser produced plasma continuum source were used for absorption measurements and the advantages of each source were compared. Experiments were undertaken to examine the radiation properties of laser produced plasmas with a view to their general use as far-ultraviolet continuum sources and a computer program was written to predict their net photon emission by Bremsstrahlung processes, with some success. Optoacoustic spectroscopy was considered as a possible technique in the far-ultraviolet with a synchrotron source; its theory was extended to include ionisation and dissociation of molecules. However, optoacoustic experiments attempted were unsuccessful because of insufficient light intensity and excessive background noise near the synchrotron.

Thesis (PhD (Physics))--University of Stellenbosch, 2006. / Carbon monoxide (CO) is a diatomic molecule of particular interest in astrophysics, due to its high abundance in interstellar space. The Fourth Positive System A1Π−X1Σ+ of CO is an important feature in the vacuum ultraviolet (VUV) region of the electromagnetic spectrum in astronomical observations, especially in high-resolution spectra recorded by satellite-based spectrographs. The interpretation of these astronomically detected spectra requires accurate laboratory wavelengths to serve as rest wavelengths and to resolve possible Doppler-shifts. Such rest wavelengths are known for the 12C16O, 13C16O and 12C18O isotopomers for all astronomically observed spectral lines of the Fourth Positive System. The only laboratory wavelengths currently available for the Fourth Positive System of the 12C17O isotopomer have been determined in a previous work carried out in our laboratory for the vibronic band A1Π(v0 = 3)−X1Σ+(v00 = 0). The present study continues this work for the other vibronic bands which have been detected astronomically, namely A1Π(v0 = 2 − 5)−X1Σ+(v00 = 0). The A1Π(v0 = 0− 1)−X1Σ+(v00 = 0) vibronic bands have also been investigated due to their probability for future astronomical detection. Rotationally-resolved spectra of these six vibronic bands were obtained by selective rovibronic laser excitation, and subsequent detection of the undispersed fluorescence, observed as a function of the excitation wavelength in the VUV. A tunable narrow-bandwidth VUV laser source is used for excitation, and the CO gas sample is introduced by supersonic expansion. Flow-cooling in the supersonic expansion to rotational temperatures roughly corresponding to temperatures in the interstellar medium simplifies and aids the spectral analysis of the spectral lines of interest. The cold conditions in the supersonic expansion facilitates a high sensitivity for detection of the low-J lines, and allows the detection of rare isotopomers of CO in natural abundance. The experimental setup has been improved in the present study by the addition of a vacuum monochromator, facilitating an improved characterisation of the VUV source. Furthermore, a number of experimental conditions have been optimised for the detection of rare CO isotopomers, significantly increasing the signals of these lines in the spectra. The combination of this increase in sensitivity and the addition of the vacuum monochromator to the experimental setup, allowed the simultaneous detection of absorption spectra with the fluorescence spectra as an additional source of information in spectral analysis. The increased sensitivity also contributed to the detection of a large number of spectral lines of interest, with some additional lines identified in the previously studied vibronic band. Spectral lines of 12C16O, 13C16O, 12C18O and 12C17O were detected in each vibronic band, allowing accurate calibration of the spectra. A total of 29 new lines of 12C17O were recorded in the six vibronic bands investigated. Additionally, 10 new singlet-triplet lines of 12C16O were recorded in the wavelength regions investigated. The new wavelengths of 12C17O have been applied to calculate consistent heliocentric velocities of a gas cloud toward the star X Persei, obtained from spectra of the different CO isotopomers taken by the Hubble space telescope.

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 138-143). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 138-143). Also available on the Internet.

Dissertation (PhD)--University of Stellenbosch, 2006. / Bibliography. Also available via the Internet.

Indiana University-Purdue University Indianapolis (IUPUI) / In the area of forensic chemistry, improved or new analysis methods are continually being investigated. One common and powerful technique used in forensic chemistry is wall-coated open-tubular column (WCOT) gas chromatography with electron ionization single quadrupole mass spectrometry (GC-MS). Improvements to and effectiveness of alternatives to this instrumental platform were explored in an array of parallel inquiries. The areas studied included the column for the chromatographic separation, the universal detection method employed, and the fragmentation method used to enhance molecular identification. Superfine-micropacked capillary (SFµPC) columns may provide an alternative to commercial packed GC columns and WCOT GC columns that combines the benefits of the larger sample capacity of packed columns and the benefits of the excellent separation capabilities and mass spectrometry (MS) flow rate compatibility of WCOT columns. SFµPC columns suffer from high inlet pressure requirements and prior reported work has required specialized instrumentation for their use. Fabrication of and chromatography with SFµPC GC columns was successfully achieved with typical GC-MS instrumentation and within the flow rate limit of a MS. Additionally, the use of higher viscosity carrier gasses was demonstrated to reduce the required inlet pressure for SFµPC GC columns. Recently, a new vacuum ultraviolet spectrometer (VUV) universal detector has been commercialized for GC. The ability of VUV detectors to acquire absorbance spectra from 125 nm to 430 nm poses a potential alternative to MS. As such, GC-VUV provides an exciting potential alternative approach to achieving excellent quantitative and qualitative analysis across a wide range of analytes. The performance of VUV and MS detectors for forensic analysis in terms of quantitative and qualitative analysis was compared. Analysis of alkylbenzenes in ignitable liquids was explored, which can be important evidence from suspected arson fires and are difficult to differentiate with MS. The VUV detector was found to have superior specificity and comparable sensitivity to the MS detector in scan mode. Addition of thermolysis (Th) as an orthogonal fragmentation pathway provides the opportunity to increase the differences between MS fragmentation patterns. Fragmentation has been widely established to aid in identification of molecules with MS by providing characteristic fragments at characteristic relative abundances. However, molecules with very similar structures do not result in sizable spectral differences in all cases with typical MS fragmentation techniques. A series of Th units were fabricated and integrated into GC-Th-MS instruments. Th-MS was conducted with the thermally labile nitrate esters across a range of instrumentation and thermal conditions.

The Polstar mission will provide for a space-borne 60cm telescope operating at UV wavelengths with spectropolarimetric capability capturing all four Stokes parameters (intensity, two linear polarization components, and circular polarization). Polstar’s capabilities are designed to meet its goal of determining how circumstellar gas flows alter massive stars' evolution, and finding the consequences for the stellar remnant population and the stirring and enrichment of the interstellar medium, by addressing four key science objectives. In addition, Polstar will determine drivers for the alignment of the smallest interstellar grains, and probe the dust, magnetic fields, and environments in the hot diffuse interstellar medium, including for the first time a direct measurement of the polarized and energized properties of intergalactic dust. Polstar will also characterize processes that lead to the assembly of exoplanetary systems and that affect exoplanetary atmospheres and habitability. Science driven design requirements include: access to ultraviolet bands: where hot massive stars are brightest and circumstellar opacity is highest; high spectral resolution: accessing diagnostics of circumstellar gas flows and stellar composition in the far-UV at 122-200nm, including the NV, SiIV, and CIV resonance doublets and other transitions such as NIV, AlIII, HeII, and CIII; polarimetry: accessing diagnostics of circumstellar magnetic field shape and strength when combined with high FUV spectral resolution and diagnostics of stellar rotation and distribution of circumstellar gas when combined with low near-UV spectral resolution; sufficient signal-to-noise ratios: ~103 for spectropolarimetric precisions of 0.1% per exposure; ~102 for detailed spectroscopic studies; ~10 for exploring dimmer sources; and cadence: ranging from 1-10 minutes for most wind variability studies, to hours for sampling rotational phase, to days or weeks for sampling orbital phase. The ISM and exoplanet science program will be enabled by these capabilities driven by the massive star science.

Io is the innermost Galilean moon of Jupiter and is considered the most volcanically active body in our solar system. With the help of the Hubble Space Telescope’s (HST) on-board Space Telescope Imaging Spectrograph (STIS), far-ultraviolet (FUV) images of Io have been captured for the past 20 years. The final goal of this project is to study the sulphur dioxide (SO2) distribution and volcanic activity on Io in FUV data taken in 1997/98 and 2013/14. The method used concerns the conversion of spectral Lyman-α intensity to SO2 density using algorithms implemented in MATLAB. As a result the SO2 distribution and volcanic activity on Io were determined and compared between the data collections. We found that the SO2 was higher in the images from 1997/98 compared to 2013/2014.

In the area of forensic chemistry, improved or new analysis methods are continually being investigated. One common and powerful technique used in forensic chemistry is wall-coated open-tubular column (WCOT) gas chromatography with electron ionization single quadrupole mass spectrometry (GC-MS). Improvements to and effectiveness of alternatives to this instrumental platform were explored in an array of parallel inquiries. The areas studied included the column for the chromatographic separation, the universal detection method employed, and the fragmentation method used to enhance molecular identification. <br><br>Superfine-micropacked capillary (SFµPC) columns may provide an alternative to commercial packed GC columns and WCOT GC columns that combines the benefits of the larger sample capacity of packed columns and the benefits of the excellent separation capabilities and mass spectrometry (MS) flow rate compatibility of WCOT columns. SFµPC columns suffer from high inlet pressure requirements and prior reported work has required specialized instrumentation for their use. Fabrication of and chromatography with SFµPC GC columns was successfully achieved with typical GC-MS instrumentation and within the flow rate limit of a MS. Additionally, the use of higher viscosity carrier gasses was demonstrated to reduce the required inlet pressure for SFµPC GC columns.<br><br>Recently, a new vacuum ultraviolet spectrometer (VUV) universal detector has been commercialized for GC. The ability of VUV detectors to acquire absorbance spectra from 125 nm to 430 nm poses a potential alternative to MS. As such, GC-VUV provides an exciting potential alternative approach to achieving excellent quantitative and qualitative analysis across a wide range of analytes. The performance of VUV and MS detectors for forensic analysis in terms of quantitative and qualitative analysis was compared. Analysis of alkylbenzenes in ignitable liquids was explored, which can be important evidence from suspected arson fires and are difficult to differentiate with MS. The VUV detector was found to have superior specificity and comparable sensitivity to the MS detector in scan mode.<br><br>Addition of thermolysis (Th) as an orthogonal fragmentation pathway provides the opportunity to increase the differences between MS fragmentation patterns. Fragmentation has been widely established to aid in identification of molecules with MS by providing characteristic fragments at characteristic relative abundances. However, molecules with very similar structures do not result in sizable spectral differences in all cases with typical MS fragmentation techniques. A series of Th units were fabricated and integrated into GC-Th-MS instruments. Th-MS was conducted with the thermally labile nitrate esters across a range of instrumentation and thermal conditions.<br>