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 (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: See full text / AFRIKAANSE OPSOMMING: Sien volteks

Optoacoustic spectroscopy is a relatively old technique first described by Alexander Graham Bell in 1881. However, over the intervening years, little use was made of the technique due to its low sensitivity. This was due to low source intensities of available infrared light sources which limited the optoacoustic signal strength. With the advent of laser infrared light sources in the 1960's, there has been a resurgence of interest in optoacoustics. No longer is low source intensity a major limitation to successful optoacoustic spectroscopy. Although adequate infrared light sources are available, the large window background signal observed in all optoacoustic systems has been the major limitation in extending trace gas detection limits to the ppb or sub-ppb level. Similarly, there has been little demonstration of the use of the optoacoustic technique in environments where mixtures of gases are present which have severe spectral overlap. This work will discuss a new windowless cell design that largely eliminates the signal background problem ubiquitous to all presently available optoacoustic cells. New methodologies will be discussed that allow analyses of mixtures to be performed even in cases where spectral overlap is severe. Limitations to both the windowless cell and the various multicomponent analysis strategies are discussed.

The objective of this thesis is to describe the development, construction and use of a new tool for optical coherent transient spectroscopy. The new tool is a frequency-switched CO₂ laser. A highly stable laser design was modified to include an intra cavity electro-optic modulator, which al lows the output of the laser to be frequency-switched. The frequency modulated output is used in spectroscopic experiments whose goals are the determination of decay rates for infrared moIecuIar transitions. The use of a frequency-switched laser is the most prom i sing means of making such measurements on nonpoIar molecules. The use of an electro-optic crystal inside a laser cavity introduces a number of fundamental problems which must be overcome before the instrument can be used to make useful spectroscopic measurements. These problems are brought about by the need for a stable laser amplitude and frequency output. The development of a novel stabilization technique to overcome these problems is documented in this thesis. Also included in this thesis is a description of the microcomputer and associated electronics necessary to integrate the laser into an experimental apparatus capable of performing signal averaging and background subtraction on raw time resolved data. The final chapters of this work describe experiments and results of measurements of the scattering cross sect ions of a nonpolar molecule with rare gas perturbers. The nonpolar molecule is SF₆ and the rare gas collision partners are Helium, Argon, and Xenon. The results indicate that the scattering cross section for state changing collisions displays a mass dependance predicted by classical collision theory. However, the measured cross sections for elastic velocity-changing collisions appears to be mass independent, which is at variance with theory.

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Resonant ionization laser ion sources are applied worldwide to increase purity and intensity of rare isotopes at radioactive ion beam facilities. Especially for heavy elements the laser wavelengths required for efficient resonant laser ionization are not only element dependent, but also vary to small degrees from isotope to isotope. Since the first operation of an actinide target at ISAC-TRIUMF in 2008, the demand for neutron-rich isotopes far away from stability has steadily increased. Those isotopes often have very low production rates so that often only a few ions per second are released. In order to study isotope shifts and hyperfine structure of silver, actinium and astatine, in-source resonant ionization spectroscopy in combination with radioactive decay detection has been applied. Despite the Doppler limited resolution, it has the advantage that it is ultra-sensitive and the atomic spectrum for the nuclear ground and isomeric states can be investigated individually. An isobaric separation has been demonstrated for 115-119Ag, where the hyperfine structure of one state showed a splitting of 22 GHz to 38 GHz while for the other state only a single peak spectrum can be resolved. For astatine and actinium, the main interest is to measure and study the optical isotope shift, which is for the first excitation step for neutron-rich isotopes in the order of IS_FES≈±3.7GHz/u for both elements, as these observables give insight into nuclear moments and shape. In addition, also the isotope shift of the second excitation step for astatine has been measured to IS_SES,At≈-1.7GHz/u. Laser spectroscopy on astatine has mainly been performed on the neutron-deficient isotopes 199,205At due to high count rates and low isobaric contamination. With the results obtained it is possible to extrapolate the required wavelength for ionizing and delivering the isotopes 221-225At which are of interest to e.g. electric dipole moment studies. / October 2017

Optical spin readout (OSR) in fullerene-based systems has the potential to solve the spin readout and scalability challenges in solid-state quantum information processing. While the rich variety of chemical groups that can be linked (covalently or not) to the fullerenes opens the possibility of making large and controlled arrays of qubits, optical methods can be used to measure EPR down to a single spin thanks to the large energy of optical photons compared to the microwave ones. After reviewing the state of the art of OSR, for which the diamond NV cen- ters constitute the benchmark, we undertake the study of fullerene-based species for OSR. An optically detected magnetic resonance (ODMR) setup was imple- mented in a commercial EPR spectrometer for this purpose. Each experimental chapter focuses on one of the molecular systems in question: a functionalised C₆₀ fullerene with a phosphonate group (C₆₀-phosphine), porphyrin-fullerene ar- chitectures (weakly, strongly and moderately coupled) and finally erbium-doped trimetallic nitride template (TNT) fullerenes (focusing on ErSc₂N@C₈₀). In the C₆₀-phosphine system, coherent optically detected magnetic resonance (ODMR) in the triplet state has been achieved. Since a large variety of organic and organometallic molecules can be attached to it both via the fullerene cage and the phosponate group, this result makes it a very useful template to study OSR molecules chemically linked to a qubit. In the porphyrin based structures, an intermediate coupling case in the form of a trimer-fullerene host-guest complex is found to allow detection of both the porphyrin and fullerene triplet sates by CW ODMR, which makes organo-metallic complexes a possible coupling route for a qubit to an OSR component. In the TNT fullerene, crystal field mixing makes the Er³⁺ inaccessible by ODMR. However, optical photons cause a mechanical rearrangement of the en- dohedral cluster which in turns impacts on the observed EPR. In particular, the dynamics of this process have been studied for the first time and hint to- wards diffusion kinetics at low pump power. An orientational selectivity has been discovered by using a polarised pump, and the time dynamics indicate the rearrangement of the matrix via difusion on a free volume around the fullerenes. This shows that the endohedral Er³⁺ in ErSc₂N@C₈₀ can probe the environment outside the cage.

Cavity enhanced absorption spectroscopies have earned themselves a place as one of the methods of choice for sensitive absorption measurements on gas-phase samples, but their application to liquid samples has so far been more limited. Sensitive short pathlength analysis of liquid samples is required for online analysis of microfluidic samples, which are processed in channels with dimensions of tens to hundreds of micrometres. Microfluidics is important for a range of applications including drug discovery and environmental sensing. This thesis explores the application of cavity enhanced absorption spectroscopies to short pathlength (0.010 mm to 2 mm) analysis of sub-microlitre volumes of liquids. Three experimental set-ups have been been examined. Firstly, a single-wavelength cavity ringdown (CRD) spectrometer operating at 532 nm was assembled using two 99.8% reflectivity mirrors. High optical quality flow cells with short pathlengths ranging from 0.1 mm to 2 mm were inserted into this cavity at Brewster’s angle. The detection limit of the set-up with each inserted flow cell was established using a concentration series of aqueous potassium permanganate (KMnO₄) solutions. For the 1 mm flow cell, a detection limit of 29 nM KMnO₄ or 1.4 x 10⁻⁴ cm⁻¹ was established. Several different types of microfluidic devices were also inserted into the cavity, and it was found that the losses arising from the inserted chip were highly dependent on the method of chip manufacture. The CRD set-up with inserted 1 mm flow cell was applied to the detection of two important species, nitrite and iron(II), via analyte-specific colourimetric reactions. Detection limits of 1.9 nM nitrite and 3.8 nM iron(II) were established. The second experimental set-up utilised broadband, supercontinuum light generated in a 20 m length of nonlinear photonic crystal fibre. Broadband mirrors with around 99% reflectivity over the wavelength range from 400 to 800 nm were used to form the cavity, and a miniature spectrometer was used to wavelength-resolve the time-integrated cavity output. Flow cells and microfluidic chips were inserted into the cavity either at normal incidence or at Brewster’s angle. This set-up was employed for reaction analysis of an iron complexation reaction with bathophenanthroline, and for a model organic reaction, the Diels-Alder reaction between anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione. The same broadband set-up was also used for pH measurements using bromocresol green indicator solution. Using dual-wavelength CRD spectroscopy, the pH sensitivity was established to be around a few milli pH units. Finally, an alternative type of cavity, formed from a loop of optical fibre has been investigated. A novel light-coupler was designed and fabricated in 365 μm core diameter multimode optical fibre. Sample designs employing both direct and evanescent wave absorption were investigated in small-core and large-core optical fibres, and the lowest detection limit of 0.11 cm⁻¹ was determined in direct absorption measurements, with a pathlength of 180 μm, using our novel light coupler in 365 μm core diameter optical fibre.