Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: C. Grant Willson. Vita. Includes bibliographical references.

No description available.

<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.

L’un des défis majeurs pour la conception des capsules de rentrée concerne la modélisation des transferts convectifs et radiatifs à la surface du véhicule. A certains points des trajectoires de rentrée super-orbitale, jusqu’à 40% du flux radiatif total émane du domaine spectral VUV (vacuum ultraviolet), or c’est dans ce domaine que les incertitudes sont les plus fortes. Ce haut niveau d’incertitudes est dû en particulier à un manque de données expérimentales fiables. Le rayonnement VUV est en effet difficile à mesurer en raison de la forte absorption de l’air et des optiques utilisées pour sa mesure. Des difficultés d’analyse supplémentaires sont causées par le fort degré d’auto-absorption et par l’élargissement spectral des raies dans le VUV. L’objectif central de cette étude était d’obtenir des spectres d’émission expérimentaux calibrés dans le VUV afin d’étudier les processus physico-chimiques dans la couche de choc qui contrôlent le flux radiatif. Plus précisément, les objectifs étaient de comparer les spectres observés parallèlement et perpendiculairement à la couche de choc, d’étudier les effets sur l’intensité des raies spectrales émises dans le VUV de l’auto-absorption et de l’élargissement spectral en fonction de la profondeur de champ radiatif (épaisseur optique). Les mesures effectuées perpendiculairement et parallèlement à la surface d’une maquette placée dans l’écoulement représentent un premier jeu de données expérimentales calibrées dans le VUV qui seront utiles pour valider les codes de calcul destinés à prédire le flux radiatif incident. Les mesures obtenues pour différentes profondeurs de champ radiatif représentent quant à elles un ensemble de données expérimentales uniques pour la validation des modèles de transport radiatif et des coefficients d’élargissement des raies. Cette étude s’appuie également sur des simulations numériques afin d’évaluer les prédictions d’un solveur d’écoulement couplé à deux schémas cinétiques à travers la comparaison des spectres mesurés avec les spectres simulés par le code radiatif Specair. Pour atteindre ces objectifs, un banc optique a été conçu et mis en place pour mesurer l’intensité du rayonnement VUV produit autour d’une maquette bidimensionnelle émoussée, avec une résolution spatiale suffisante pour résoudre le profil d’émission dans la couche de choc. La résolution spatiale a été choisie de façon à pouvoir effectuer des mesures du rayonnement dans les zones d’équilibre et hors équilibre de la couche de choc. Un deuxième système a été conçu pour obtenir des mesures du rayonnement VUV incident sur la surface de la maquette. Ce système est constitué d’un hublot placé sur la surface de la maquette et d’un miroir logé à l’intérieur de la maquette pour transmettre le rayonnement vers le système de détection. La profondeur du champ radiatif peut être variée en modifiant la longueur de la maquette, ce qui change l’épaisseur de la couche de choc observée. Le tunnel à détente X2 a été utilisé pour créer les écoulements à haute enthalpie nécessaires pour produire les couches de choc émissives. Deux conditions d’écoulement ont été générées pour cette étude de façon à reproduire des vitesses équivalentes de vol de 10 et 12.2 km/s. Le système spectroscopique utilisé pour ces études comprend un spectromètre McPherson NOVA 225 sous vide couplé à une caméra ICCD Andor iStar de réponse renforcée dans le VUV. Un tube optique scellé par une fenêtre en fluorine a été installé pour prolonger le trajet optique sous vide jusqu’à la maquette de façon à éliminer l’absorption par l’oxygène moléculaire. Le système spectroscopique a été calibré in situ avec une lampe à deutérium placée à l’endroit de la couche de choc rayonnante. L’intensité spectrale incidente sur la surface de la maquette, intégrée entre 115 et 180 nm, est de 0,744 W/cm²sr pour une vitesse d’écoulement de 10 km/s et 12,3 W/cm²sr à 12.2 km/s. [...] / A major design challenge for re-entry capsules lies in the modelling of convective and radiative heat transfer to the surface of the vehicle. At certain points on superorbital re-entry trajectories, up to 40% of the total radiative heat flux is contributed by the vacuum ultra-violet (VUV) spectral range and it is in this spectral range that the largest uncertainties lie. The high level of uncertainty in the VUV is a result of a lack of published experimental data due to difficulties encountered in measuring radiation in the VUV, such as strong absorption by most optical materials and air. Additional complexities of the VUV spectral range include its strongly self-absorbing nature and spectral line broadening. The primary goal of this study was to obtain calibrated spectral measurements in the VUV that enable the investigation of physical processes occurring in the shock layer that influence the incident radiative heat flux. In particular, the issues to be investigated were the variation in spectral radiance observed across a shock layer compared to the spectral radiance measured through the surface, the effects of self-absorption on spectral line intensity and the broadening of spectral lines in the VUV as a function of depth of radiating flow field. The measurements made across and through the surface of a model provide the first set of calibrated experimental results for the validation of computational codes used to predict incident radiative heat flux. Measurements made with a varying depth of radiating flow field provide a unique set of experimental data for the validation of radiation transport models and broadening coefficients. This study also used computational simulations to investigate the accuracy of a flow field solver coupled with two reaction rate schemes and compared the spectra produced using Specair with experimentally measured values. To achieve these goals, an optical system was designed to measure the VUV radiative emission produced around a blunt two-dimensional model in a spatially resolved manner across the shock layer. Spatial resolution allowed for spectral measurements to be made in both the equilibrium and non-equilibrium parts of the shock layer. A second optical system was designed to obtain measurements of VUV radiation incident on the surface of the model. This system incorporated a window in the surface with a mirror housed within the model to deflect the radiation out of the test section and into the detection system. To effectively vary the depth of the radiating flow field, the length of a two-dimensional model was varied, changing the depth of the shock layer being observed. The X2 expansion tube was used to create the high enthalpy flows required to produce radiating shock layers. Two flow conditions were created for this study that represented flight equivalent velocities of 10.0 km/s and 12.2 km/s. The spectroscopy system utilized for this study consisted of an evacuated McPherson NOVA 225 spectrometer coupled to an Andor iStar VUV enhanced intensified charge coupled device. An evacuated light tube sealed with a magnesium fluoride window was required to extend the evacuated light path to the model and avoid any absorption by molecular oxygen. An in-situ calibration of the VUV spectroscopy system was conducted using a deuterium lamp located in the position of the radiating shock layer. The integrated incident spectral radiance measured through the surface of the model between 115 nm and 180 nm was 0.744 W/cm2 sr for the 10.0 km/s condition and 12.3 W/cm2sr for the faster 12.2km/s condition. [...]

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