<p> In Part I of this thesis, the design, construction, and calibration of a twenty-one foot off-plane Eagle vacuum spectrograph, a Lyman source, and predispersion unit are described.</p> <p> In Part II, the results of an investigation of the electronic absorption spectra of the cyanogen halides, obtained with the apparatus described in Part I, are given. Several electronic absorption systems have been observed for each of the cyanogen halides. These have been correlated and assigned to electronic transitions. Vibrational analyses have been made and the excited state dimensions have been determined by a quantitative application of the Franck-Condon principle for two absorption systems of each of the cyanogen halides.</p> / Thesis / Doctor of Philosophy (PhD)

A paucity of literature exists on the Independent System analysis of adjacent, parallel transition dipoles. Applying this theory and certain spectral information semiemperical calculations were made to predict absorption profiles and band intensities. To aid in the assignment of the 7*+7 absorption bands it was necessary to obtain the vacuum ultraviolet spectra of cyclohexane and cyclohexene. Because the spectra of these molecules contained sharp, atomic-like absorption bands a Rydberg series could be fitted to certain absorptions, thus the determination of their ionization potentials. Using Independent System analysis profiles and intensities of 7*+q-- absorption bands ins 'several methyl substituted 1,4- cyclohexadienes and isotetralin were predicted where general agreement was found with observed experimental spectra.

Thesis (MSc (Physics))--University of Stellenbosch, 2005. / A tunable vacuum ultra-violet (VUV) laser source was recently developed for VUV spectroscopy using state selective excitation and total fluorescence detection. The VUV laser source makes use of a four-wave mixing process to provide tunable VUV radiation for the electronic excitation of the molecules. The theory of four-wave mixing, with the emphasis on parameters that are important for our experimental setup to generate efficient tunable VUV radiation is discussed. The experimental setup, and in particular the metal vapor heat-pipe, which provides Mg vapor as the nonlinear medium, is described. New diagnostic equipment described in this work was added to the experimental setup. This equipment was characterized and utilized together with the existing setup. The additional diagnostic equipment introduced enabled us to measure the tunable VUV output of the source (using a VUV monochromator), making it possible to significantly improve the efficiency of the existing tunable VUV laser source.

Thesis (PhD)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: A tunable narrow-bandwidth laser source combined with a supersonic gas jet as sample is wellsuited for obtaining high-resolution spectra of cold isolated molecules and complexes. In the present study such a laser source in the vacuum ultraviolet was applied to the spectroscopic investigation of rare carbon monoxide (CO) isotopomers and CO-noble gas van der Waals complexes in supersonic gas pulses seeded with natural CO gas. Tunable coherent vacuum ultraviolet radiation was generated by two-photon resonant fourwave sum-frequency mixing of two pulsed dye laser beams in a magnesium vapour medium. Laser induced fluorescence excitation spectra of the A(v'=3)-X(v"=0) vibronic band of CO molecules in a noble gas (neon or argon) jet were obtained by measuring the total undispersed fluorescence from the irradiated sample volume in dependence of the excitation wavelength. The dynamics of the flow-cooling process in the supersonic jet were investigated and the experimental parameters optimised using the rotational temperature of 12C160as determined from rotational line intensities. Rotational temperatures as low as 2 ± I K were observed. Spectroscopic detection of the rare 12C170and 12C180isotopomers was facilitated by the low rotational temperature and high spectral resolution. Six rotational lines of 12C170and four of 12C180were detected in the A(v'=3)-X(v"=0) vibronic band. This demonstrates the low detection limit (circa 3 parts per million) obtained in the experiment. The line wavelengths were determined to an accuracy of 0.2 pm using the well-documented 12C160and 13C160lines for calibration. The spectral results on 12C170are, to our knowledge, the first rotationally resolved laboratory measurements published on the A-X band of this isotopomer. Accurate wavelength data of the stable isotopomers of CO is of importance in the interpretation of astrophysical observations of CO in the interstellar medium. The newly determined 12C170wavelengths were successfully applied to a recent problem in astrophysics (Astrophys. J. Lett. 2003). The conditions in a supersonic jet facilitate the study of weakly bound van der Waals complexes, of which CO-noble gas complexes are prototypes. However, there is no experimental data available on the electronic excitation spectra of the CO-noble gas complexes, lying in the vacuum ultraviolet region. In the present experiment evidence of extensive complexation of the CO in the noble gas jet has been found, but in the spectral region around the A(v'=3)-X(v"=O) band of CO no distinct spectral features that could be associated with these complexes were observed. Having considered the existing knowledge on CO and CO-noble gas complexes and experimental studies on the excitation and dissociation dynamics of Iz-noble gas complexes, we regard complex induced inter-system crossing or electronic predissociation as the most likely causes for these observations. The results on the rare CO isotopomers demonstrate the potential of our experimental setup for high-resolution, isotope and state selective spectroscopy in the vacuum ultraviolet with a high sensitivity for fluorescent species. The availability of the now well-characterised experimental setup in our laboratory opens the way for further investigation of molecular or complex species with spectroscopic features in the vacuum ultraviolet region. / AFRIKAANSE OPSOMMING: Vakuum ultraviolet laser spektroskopie van CO molekules in 'n supersoniese gasstraal: 'n Afstembare smal bandwydte laserbron en 'n supersoniese gasstraal as monster is 'n geskikte kombinasie vir hoë-resolusie spektroskopie van geïsoleerde afgekoelde molekules en komplekse. In hierdie studie is so 'n laserbron in die vakuum ultraviolet gebruik in die spektroskopiese ondersoek van skaars koolstofmonoksied (CO) isotopomere en CO-edelgas van der Waals komplekse in supersoniese gaspulse wat 'n klein persentasie natuurlike CO gas bevat. Afstembare koherente vakuum ultraviolet lig is verkry deur twee-foton resonante vier-golf som-frekwensie vermenging van twee gepulseerde kleurstoflaserbundels in 'n magnesiumdamp medium. Laser-geïnduseerde fluoressensie opwekkingspektra van die A(v'=3)-X(v"=0) vibroniese band van die CO molekules in die edelgasstraal (neon of argon) is uitgemeet deur die totale fluoressensie van die beligte gasmonster, sonder golflengteskeiding, te meet as funksie van die opwekkingsgolflengte. Die dinamika van die vloeiverkoelingsproses in die supersoniese gasstraal is ondersoek en die eksperimentele parameters geoptimeer deur gebruik te maak van die rotasionele temperatuur van 12Cl60 soos bepaal uit die intensiteitsverhoudings van die rotasielyne. Rotasionele temperature tot so laag as 2 ± 1 K is waargeneem. Spektroskopiese waarneming van die skaars 12C170 and 12Cl80 isotopomere is moontlik gemaak deur die lae rotasionele temperatuur en die hoë spektrale resolusie. Ses rotasielyne van 12C170 en vier van 12C180 is waargeneem in die A(v'=3)-X(v"=0) vibroniese band. Dit demonstreer die lae deteksielimiet (ongeveer 3 dele per miljoen) wat bereik kon word. Die golflengtes van die lyne is bepaal met 'n akkuraatheid van 0.2 pm deur die bekende lyne van 12C160en 13C160vir kalibrasie te gebruik. Die resultate ten opsigte van 12C170 is sover vasgestel kon word die eerste rotasioneel-opgeloste laboratorium metings van die A-X band van hierdie isotopomeer. Akkurate golflengte data vir die stabiele CO isotopomere is van belang vir die interpretasie van die astrofisiese waarnemings van CO in die interstellêre medium. Die nuwe 12C170 golflengtes is suksesvol aangewend in die oplossing van 'n onlangse interpretasieprobleem in astrofisika (Astrophys. J. Lett. 2003). Die toestande in 'n supersoniese gasstraal maak die bestudering van swak-gebonde van der Waals komplekse moontlik. Hoewel CO-edelgas van der Waals komplekse as prototipes beskou word, is daar geen eksperimentele data beskikbaar oor die elektroniese opwekkingspektra van hierdie spesies, wat in die vakuum ultraviolet gebied lê, nie. In hierdie studie is daar eksperimentele getuienis gevind vir uitgebreide kompleksering van CO in die edelgasstraal, maar in die spektraalgebied rondom die A(v'=3)-X(v"=O) band van CO is geen duidelike spektrale kenmerke wat met hierdie komplekse geassosieer kan word, waargeneem nie. Na oorweging van die bestaande kennins oor CO en CO-edelgas komplekse en eksperimentele studies oor die opwekking en dissosiasie-dinamika van Iz-edelgas komplekse, beskou ons kompleksgeïnduseerde intersisteemoorgange of elektroniese predissosiasie as die waarskynlikste redes vir hierdie waarnemings. Die resultate oor die skaars CO isotopomere toon die potensiaal van ons eksperimentele opstelling vir hoë-resolusie, isotoop- en toestandselektiewe spektroskopie in die vakuum ultraviolet met uitstekende sensitiwiteit vir fluoresserende spesies. Die beskikbaarheid van hierdie nou deeglik gekarakteriseerde eksperimentele opstelling in ons laboratorium maak verdere ondersoek na molekulêre of kompleks-spesies met spektroskopiese kenmerke in die vakuum ultraviolet moontlik.

Inductively-Coupled Plasma Optical Emission Spectrometry (ICP-OES) is evaluated as a method for the selective determination of several non-metals which emit light in the Vacuum Ultraviolet (VUV) region of the spectrum. In this study, emphasis is placed on those elements which are totally unobservable with standard techniques or have very weak lines in the UV-VIS region of the spectrum. The sensitivity and accuracy of the apparatus and methods devised allows the determination of empirical formulas of gas chromatographic effluents. The results of this study indicate that the background emission of the ICP in the VUV is low level and nearly constant over the entire spectral region investigated (125 - 185 nm.). Promising analytical lines for oxygen, nitrogen, chlorine, bromine, and carbon are also observed in this region. A progression of four experimental configurations were constructed, employing a purged optical path and a unique coolant tube design. The last of these configurations has the capability of spatial resolution of individual portions of the discharge so that emission maps and profiles could be constructed. The results of the maps generated indicate that the region of highest emission intensity is always centered in the discharge. However, the vertical position of this region is found to be dependent upon r.f. power and argon flow rates. Detection limits in the low nanogram region are observed for each non-metal. The dynamic range for each element is in excess of 10⁴ and the selectivity ratio versus carbon is above 100 in each case. A method was developed for determining the elemental composition of the effluents of a GC. Using internal standards, the method is independent of the weight of each component eluted thus sampling errors are eliminated. The average relative errors in multielement analysis are 0.89%, 0.75%, 2.1%, 0.55%, and 0.64% for the percent carbon, oxygen, nitrogen, chlorine, and bromine, respectively.

This thesis describes an experimental study of high intensity, pulsed, optically pumped, far-infrared (FIR) lasers. The work was motivated by the need for a radiation source for the measurement of the ion temperature in magnetically confined, high temperature plasmas (e.g. tokamak plasmas), using Thomson scattering. Constraints imposed by the plasma parameters, the scattering geometry and available detector sensitivities lead to the requirement of a radiation source wavelength between 30μm and 1mm and a source power . 1 MW in a bandwidth 60 MHz. Results are presented for a 496μm, 500 watt, methyl fluoride (CH₃F) cavity laser, with a bandwidth of and < 30MHz, which was optically pumped by a 9.55μm CO₂ laser. Results are also presented for an optically excited mirrorless, super-radiant, CH₃F laser, which generated over 0.6MW of FIR radiation within a bandwidth of about 300MHz. The performance of this laser has also been simulated by a computer model, which allows the optimum operating parameters to be predicted. An assembly constructed on the principle of the injection laser, in which low power narrow-band oscillator radiation is used to control the output of a super-radiant system, has been used to generate 250 kW of 496 andmu;m radiation, with a bandwidth of < 60 MHz. Investigations of the FIR output from heavy water vapour (D₂O) in a super-radiant laser assembly, optically excited by several different CO₂ laser wavelengths, have resulted in the generation of 60 ns (FWHM) pulses of FIR radiation with average powers of 1.3, 9.2 and 15.8MW, at wavelengths of 385, 119 and 66μm, respectively. All these lasers were found to have a higher CO₂ to FIR photon conversion efficiency than the 496μm CH₃F laser. In addition, the energy level spacing in D₂O is such that the molecule can generate narrow bandwidth radiation more readily than the CH₃F molecule. From this work it is concluded that an injection laser assembly, similar to that used with CH₃F, but containing D₂O vapour, optically pumped by a 9.26μm CO₂ laser and generating several megawatts of 385μm radiation, would satisfy the source requirements mentioned above.

Bibliography: leaves [250]-268 / 268, ca. 130 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physics, 1983

The Z-pinches in a vacuum spark can be classified into slow, fast and superfast according to their pinch durations. Their emission characteristics are investigated in the visible, ultraviolet and the X-ray wavelengths. The plasma during a fast pinch was found to have an electron temperature between 100 and 600eV. The superfast pinch resulted in a minute cylindrical plasma approximately 40 μm in diameter, with an electron temperature of 1 to 4keV and a lifetime of less than 4ns. The slow and the fast pinch were found to be in agreement with the theoretical results predicted by a shock wave model. The formation of the superfast pinch and its associated high density and temperature were explained as the results of magnetohydrodynamic instability. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The large band gap (approximately 11.5-12.1 eV) and high transmission of calcium fluoride (CaF2) crystal in the ultraviolet (UV) and vacuum ultraviolet (VUV) region makes it an important material for optics for laser applications in UV. However, CaF2 degrades during long exposure to UV irradiation due to defect generation. The formation of selftrapped excitons (STE) is considered the first step in defect generation. In this project the possibility of observing STE states in CaF2 using a narrow bandwidth tunable VUV laser source is investigated. This is the first spectroscopy study of an alkaline earth fluoride using VUV tunable laser radiation instead of a fixed wavelength laser. The use of a VUV tunable laser source has potential for determining the energies of the STE states, which are unknown. Our main objective is addressed by developing techniques to measure absorption spectra of pure and doped CaF2 samples, using a VUV scanning monochromator and a tunable VUV laser, and by doing a literature study. The results obtained with the scanning monochromator show absorption features in 126-180 nm range of all our samples. These vary for different samples and correlate with information from the supplier on the samples’ fluorescence spectra. Total absorption of the VUV light by CaF2 in the 115-126 nm range is observed. With the narrow bandwidth tunable laser light, absorption spectra were obtained in the range of 143-146.7 nm of all our CaF2 samples. No significance peaks which can be related to the STE states in CaF2 were observed in the VUV laser absorption spectra, but the results are valuable to improve the technique. The conclusion is that either a different spectral range or fluorescence detection can be investigated in future. / AFRIKAANSE OPSOMMING: Die groot bandgaping (ongeveer 11.5-12.1 eV) en hoë transmissie van kalsiumfluoried (CaF2) kristal in die ultraviolet (UV) en die vakuum ultraviolet (VUV) gebied maak dit ’n belangrike materiaal vir optika vir laser toepassings in die UV. CaF2 degradeer egter gedurende langdurige blootstelling aan UV lig as gevolg van die generering van defekte. Die vorming van ’n elektron-holte paar wat deur die kristalstuktuur gestabiliseer word teen rekombinasie (self-trapped excitons, afgekort STE) word beskou as die eerste stap in defek generering. In hierdie projek word die moontlikheid ondersoek om STE toestande in CaF2 waar te neem deur die gebruik van ’n afstembare VUV laserbron met emissie in ’n smal spektrale band. Dit is die eerste spektroskopiese studie van ’n aardalkali-fluoried deur die gebruik van afstembare VUV laserlig in plaas van ’n vaste golflengte laser. Die gebruik van ’n afstembare VUV laserbron het potensiaal vir die bepaling van die energieë van die STE teostande, wat onbekend is. Ons hoofdoel word aangespreek deur die ontwikkeling van tegnieke vir die meet van absorpsie spektra van suiwer en gedoteerde CaF2 monsters met behulp van ’n VUV skanderende monochromator en ’n afstembare VUV laser, en deur ’n literatuurstudie. Die resultate wat behaal is met die skanderende monochromator toon die absorpsieprofiele van al ons monsters in die 126-180 nm spektrale gebied. Die absopsieprofiele varieer vir die verskillende monsters en korreleer met die inligting van die verskaffer oor die fluoressensie spektra van die monsters. Totale absorpsie van die VUV lig deur CaF2 in die 115-126 nm gebied is waargeneem. Met die smalband afstembare laserlig is absorpsie spektra in die 143-146.7 nm gebied vir al ons CaF2 monsters verkry. Geen beduidende pieke wat verband hou met die STE toestande in CaF2 is waargeneem in die VUV laser absorpsie spektra nie, maar die resultate is waardevol vir die verbetering van die tegniek. Die gevolgtrekking is dat of ’n ander spektraalgebied of fluoressensiedeteksie in die toekoms ondersoek kan word.

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.