Doctoral Degrees (Physics)

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Browsing Doctoral Degrees (Physics) by browse.metadata.advisor "Du Plessis, Anton"

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    Femtosecond pump probe spectroscopy of light harvesting complexes and Phthalocyanines
    (Stellenbosch : Stellenbosch University, 2011-12) Ombinda-Lemboumba, Saturnin; Du Plessis, Anton; Steenkamp, Christine M.; Rohwer, Erich G.; Stellenbosch University. Faculty of Science. Dept. of Physics.
    ENGLISH ABSTRACT: The generation of ultrafast light pulses and the development of time resolved spectroscopic techniques, such as the femtosecond pump probe spectroscopy technique, have facilitated the study of ultrafast energy transfer in the photosynthetic systems of green plants and photodynamic therapy drugs. It has allowed the investigation of biological and chemical processes that take place on the ultrafast timescale and has allowed us to obtain spectral and kinetic information on energy transfer. In addition, it has allowed time resolved experiments in which the transient absorption of species under investigation was observed and has elucidated molecular dynamics. In the present work this was done with a temporal resolution of approximately 200 fs and covering a pump-to-probe delay range of 300 fs to 2 ns. The main aims of this study were to characterise the femtosecond pump probe spectroscopy system, to investigate the energy transfer in the natural light harvesting complex II (LHC II) in view of future expansion to the study of synthesized arti cial functional light harvesting complexes and nally to study ultrafast processes in zinc phthalocyanine (ZnPc) systems. In photosynthetic organisms, LHC II is the most abundant light harvesting complex and it plays an important role in light harvesting and photoprotection. The light energy is absorbed by light harvesting complexes and transferred to a reaction centre (RC) in an ultrafast timescale. Phthalocyanines are a new class of photosensitiser used for photodynamic therapy. These drugs are used to treat small and super cial tumours. The energy transfer from the singlet excited state to the triplet excited state occurs on an ultrafast timescale. However, recent work done on zinc phthalocyanine has proved that the determination of the ultrafast component remains a challenge. Several ultrafast studies carried out on ZnPc in solvents have been not only unsuccessful to give a clear picture of the ultrafast dynamics but have also produced divergent results. In this study, a characterisation of the femtosecond pump probe spectroscopy setup was done. The samples under investigation were probed by a white light continuum. The generation of the white light continuum introduced chirp, which in uenced the temporal evolution of the transient absorption results. The technique used to correct the chirp introduced by white light generation is discussed in detail. Our femtosecond pump probe spectroscopy setup was benchmarked by using a well known dye, namely malachite green. In addition, the investigation of the transient absorption change of LHC II, an active component in photosynthesis, as extracted from spinach leaves and the ultrafast dynamics of a promising photosensitiser ZnPc in dimethyl sulfoxide (DMSO) as well as in dimethyl formamide (DMF) was done. The spectral and dynamic results obtained using these three samples are described and exponential ts to the absorbance decay curves used to estimate the timescales of the energy transfer processes are presented. In this experiment, the dynamics and measured time constants related to the energy transfer between the different types of chlorophyll in LHC II was monitored, whereas with ZnPc, the dynamics and the measured time constants associated with solvation dynamics and vibrational relaxation was examined.
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    Resonant ionization spectroscopy for laser isotope separation of zinc isotopes
    (Stellenbosch : Stellenbosch University, 2021-12) De Bruyn, Andre; Steenkamp, Christine M.; Rohwer, Erich G.; Du Plessis, Anton; Stellenbosch University. Faculty of Science. Dept. of Physics.
    ENGLISH ABSTRACT: The vast zinc (Zn) reserves in South Africa are currently being underutilized, as the Zn ore refinement and isotope enrichment occurs abroad. The enrichment process most commonly used thus relies only on mass separation techniques and is therefore limited when separating isotopes of similar masses like 68Zn and 67Zn. Pure 68Zn and 67Zn are important stable nuclides in the medical industry as these isotopes are used for production of gallium-based radiopharmaceuticals used in positron emission tomography (PET) and single-photon emission computerised tomography (SPECT) scans. Additionally, depleted 64Zn is used in the cooling water of nuclear reactors for the prevention of stress corrosion cracking as well as limiting the formation of cobalt radioisotopes. This study aimed to investigate, model and optimize resonant ionization spectroscopy (RIS) schemes for the Zn isotopes 68Zn and 67Zn that are suitable for laser-based enrichment of these isotopes from natural Zn. This study reports on the development and implementation of the first experimental RIS system combined with a time-of-flight mass spectrometer at Stellenbosch University. This system was used to investigate a resonance ionization scheme that has potential for laser-based enrichment of Zn isotopes from a natural Zn sample. The ionization scheme was chosen by considering transition wavelengths, the hyper fine splitting of 67Zn, and transition strengths of intermediate levels. The effect of physical conditions and laser parameters was experimentally investigated. The experimental results were complemented by a rate equation model of the RIS scheme developed in this study. The experimental measurements included laser induced fluorescence (LIF) from both the first and second intermediate levels in the RIS scheme. The experimental LIF results contributed to optimization of the experiment and refining the rate equation model by confirming the laser bandwidth and helping to estimate an unknown transition probability. The experimental RIS measurements confirmed the model results for the existing experimental conditions, including the effects of laser tuning, pulse timing and laser pulse energy. The limiting factor to the isotope selectivity of the RIS experiment was the bandwidth of the dye laser used for the first excitation step. The simulated results of the rate equation model that was developed in this study was tested against experimental results and was found to be in good agreement. The model was also applied to conditions which could be found in industrial scenarios. The results indicated that when using a commercially available narrow bandwidth Ti:sapphire laser ( 300 MHz) it is possible to achieve 85% enrichment of 67Zn if the Zn vapour is suffciently cooled ( 100 K).