<p>This thesis is based on a selection of six different experimental techniques used for studies in atomic and molecular physics. The techniques analysed in the thesis are compared to find similarities in strategies and ways to avoid sources of error.</p><p>Paper 1 deals with collision based spectroscopy with 60 keV Xe6+ ions on sodium and argon gas targets. Information on energy of Rydberg states in Xe5+ is unveiled by optical spectroscopy in the wavelength range from vacuum ultraviolet (VUV) to visible. In paper 2, the fast ion-beam laser spectroscopy (FIBLAS) is adapted for measuring hyperfine structure of barium isotopes in an isotopically pure ion-beam. This techniques involves changing the isotope during the measurement to minimize sources of error in measurement and enhance the signal from lesser abundant isotopes. The FIBLAS technique is used in paper 3 to study samarium ions. The ions are optically pumped and the recorded optical nutation is used to measure transition probabilities. This technique eludes the difficulties inherent in relative intensity measurements of all the radiative transitions from an excited state. In Paper 4, optical emission spectroscopy is used in the VUV region to study noble gas mixture discharges. The source of the emission bands near the resonance lines of krypton and xenon are found to be heteronuclear dimers. In paper 5, radiation from a pulsed argon plasma with admixture of nitrogen is studied with time resolved spectroscopy in the VUV and ultraviolet wavelength ranges to investigate the mechanism of energy transport. A metastable state of atomic argon is found to be an important source of energy to many radiative processes. In Paper 6, photoelectron spectroscopy (PES) on thiophene, on 3-bromothiophene and on 3,4-dibromothiophene using time-of-flight photoelectron-photoelectron coincidence technique and conventional PES to investigate the onset of double ionisation compared to the onset of single ionisation in molecules.</p>

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The measurement of radical species in the atmosphere has far reaching implications. For example, it is necessary to both understand and improve our knowledge of radicals in the atmosphere to better inform the models which in many cases are the best way of predicting future air quality and climate change. Although many of these models are often not fully representative of all the processes occurring, they are the current best estimate based on the knowledge available, and can be useful in informing and directing future policy. The numerous, varied and interlinked cycles in the atmosphere are complex and only by obtaining data on specific species can accurate concentrations be retrieved and fed back into the models to improve their accuracy. This work is concerned with the development and application of an ultrasensitive absorption spectroscopy technique to the problem of detection of the peroxy radical, HO₂. Noise Immune Cavity Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS) combines cavity enhancement techniques (in order to increase the path length) with frequency and wavelength modulation techniques (in order to reduce the noise). Following a discussion of the current detection methods used by atmospheric scientists to accurately measure and quantitative concentrations, some preliminary work on the detection of ammonia by a simple cavity enhanced absorption setup is presented. Pressure broadening and shift results were obtained for a number of ammonia transitions in the near infrared region, broadened by He, Ne, Ar, Xe, O₂ and N₂. The bulk of the work concentrates on the implementation of the NICE-OHMS technique, presenting the first results with the use of an external cavity diode laser and a ring shaped cavity. A sensitivity of 4 x 10⁻¹¹ cm⁻¹ Hz⁻^1/2 is obtained on an individual rovibrational transition of methane at 6610.063 cm⁻¹, along with a selection of other data from the atmospherically important molecules methane, nitrogen dioxide and carbon dioxide, highlighting the broad wavelength range over which the instrument can operate. Finally, the NICE-OHMS technique is used to probe HO₂ radicals formed through the photolysis of a Cl₂/CH₃OH/O₂ mixture. Following the creation and detection of HO₂ radicals in the cavity, and based on the optimum sensitivity outlined above, a minimum concentration of 1 x 10⁹ molecules cm⁻³ has been demonstrated.

This thesis improves our understanding of the charge-transfer dynamics in organic materials employed in dye-sensitized and nanotube-thiophene solar cells. For the purpose of this work, a femtosecond transient absorption spectroscopy setup was built. Additionally, microsecond transient absorption spectroscopy was utilised to explore dynamics on a longer time-scale. In the first study, the dependence of dye regeneration and charge collection on the pore- filling fraction (PFF) in solid-state dye-sensitized solar cells (DSSCs) is investigated. It is shown that while complete hole transfer with PFFs as low as ~30% can be achieved, improvements beyond this PFF are assigned to a stepwise increase in the charge-collection efficiency in agreement with percolation theory. It is further predicted that the chargecollection efficiency saturates at a PFF of ~82%. The study is followed by an investigation of three novel hole-transporting materials for DSSCs with slightly varying HOMO levels to systematically explore the possibility of reducing the loss-in-potential and thus improving the device efficiency. It is shown that despite one new HTM showing a 100% hole-transfer yield, all devices based on the new HTMs performed worse than those incorporating spiro-OMeTAD. Furthermore, it is demonstrated that the design of the HTM has an additional impact on the electronic density of states present at the TiO₂ electrode surface, and hence influences not only hole- but also electron-transfer from the sensitizer. Finally, a study on a polymer-single-walled carbon nanotube (SWNT) molecular junction is presented. Results from femtosecond spectroscopic techniques show that the polymer poly(3-hexylthiophene) (P3HT) is able to transfer charges to the SWNT within 430 fs. Addition of excess P3HT polymer leads to long-lived free charges making these materials a viable option for solar cells.

This thesis set out to investigate light storage based on dynamic electromagnetically induced transparency (EIT) in a room-temperature atomic ensemble of rubidium as a means to provide a quantum memory for single-photons created by a single rubidium atom coupled to a high-finesse optical resonator. Setting up the light storage medium presented a new addition to the research group's portfolio of experimental techniques and led to investigations of EIT, slow light and stored light in warm rubidium-87 vapour. Lambda level schemes connecting Zeeman or hyperfine substates on the D₁ and D₂ lines were addressed in rubidium vapour cells containing different buffer gases and different isotopic fractions of rubidium-87 and rubidium-85. Single beam spectroscopy with a weak probe was used to characterise the vapour cells. A numerical method to fit the D line spectrum to a theoretical model to include isotopic fractions and collisional broadening of a buffer gas has been implemented. Temperature and isotopic fractions could be reliably extracted from the fit parameters. For an offset-stabilisation of two lasers to address a lambda level scheme connecting the two different hyperfine groundstates in rubidium a phase locked loop including a frequency divider has been designed and implemented. Light storage and retrieval has been demonstrated using a Zeeman scheme on the D1 line. Two microsecond long classical light pulses containing one million photons on average were stored and retrieved with an efficiency of 15&percnt; after a delay of one microsecond. Several methods of attenuating the strong co-propagating control laser beam to allow for lowering the signal pulse intensity in future experiments are discussed.

In this work we study thin epilayers of new antiferromagnetic semimetal CuMnAs by time- resolved magneto-optical experiments. In 10 nm layers of CuMnAs, we observed a harmonic dependence of the dynamical magneto-optical signal on the orientation of probe pulse linear polarization. This shows that in this 10 nm layer there is an in-plane uniaxial magnetic anisotropy which can be detected due to a quadratic magneto-optical effect - magnetic linear dichroism. From the measured data we also estimated the Néel temperature and the spectral variation of the magneto-optical coefficient describing the magnitude of the magnetic linear dichroism in this sample.

The design of dyes for NiO-based dye-sensitized solar cells (DSSCs) has drawn attention owing to their potential applications in photocatalysis and because they are indispensable for the development of tandem dye-sensitized solar cells. The understanding of the electron transfer mechanisms and dynamics is beneficial to guide further dye design and further improve the performance of photocathode in solar cells and solar fuel devices. Time-resolved spectroscopy techniques, especially femtosecond and nanosecond transient absorption spectroscopy, supply sufficient resolution to get insights into the charge transfer processes in p-type dye sensitized solar cell and solar fuel devices. In paper I-V, several kinds of novel organic “push-pull” and inorganic charge transfer dyes for sensitization of p-type NiO, were systematically investigated by time-resolved spectroscopy, and photo-induced charge transfer dynamics of the organic/inorganic dyes were summarized. The excited state and reduced state intermediates were investigated in solution phase as references to confirm the charge injection and recombination on the NiO surface. The charge recombination kinetics is remarkably heterogeneous in some cases occurring on time scales spanning at least six orders of magnitude even for the same dye. In this thesis, we also proposed a novel concept of solid state p-type dye sensitized solar cells (p-ssDSSCs) for the first time (paper VI), using an organic dye P1 as sensitizer on mesoporous NiO and phenyl-C61-butyric acid methyl ester (PCBM) as electron conductor. Femtosecond and nanosecond transient absorption spectroscopy gave evidence for sub-ps hole injection from excited P1 to NiO, followed by electron transfer from P1●- to PCBM. The p-ssDSSCs device showed an impressive 620 mV open circuit photovoltage. Chapter 6 (paper VII) covers the study of electron transfer mechanisms in a covalently linked dye-catalyst (PB-2) sensitized NiO photocathode, towards hydrogen producing solar fuel devices. Hole injection from excited dye (PB-2*) into NiO VB takes place on dual time scales, and the reduced PB-2 (PB-2●-) formed then donates an electron to the catalyst unit.  The subsequent regeneration efficiency of PB-2 by the catalyst unit (the efficiency of catalyst reduction) is determined to ca. 70%.

Weak interactions in an atomic system by external electromagnetic fields or nucleon-nucleon interaction cause perturbations in the wave-function and energy levels of electrons, which allow for transitions that are otherwise forbidden. Of particular interest are magnetic dipole (M1) transitions, Stark-induced transitions, and parity non-conserving (PNC) transitions. The PNC interaction in the hyperfine ground states is dominantly due to the anapole moment of the nucleus and there has been up-to-date only one such measurement carried out in any system; the Boulder group's ground-breaking measurement of the anapole moment in atomic cesium in 1997. Their result derived from two different hyperfine transitions, however, did not agree with the meson-coupling model from high energy physics experiments. Therefore, it is important to revisit the anapole moment through another method to cross-check the Boulder group's measurement. Our goal is to excite the nuclear-spin-dependent (NSD) PNC ground hyperfine transitions in cesium via radio-frequency (rf) and Raman excitation to directly determine the anapole moment. I present our progress toward measurement of the NSD transition in an atomic Cs beam geometry. We have developed a broadband rf cavity resonator to strongly suppress the magnetic dipole (M1) transition while enhancing the forbidden PNC electric dipole (E1) transition. We employed an injection locking scheme to generate a pair of phase-coherent Raman lasers far detuned from the cesium D2 line (852 nm) with a 9.2 GHz frequency difference. I report various measurement data from atomic signal via rf and Raman excitation. In the next generation of measurements, we will carry out interference experiments between rf and Raman transitions by varying the phase relations of the rf and Raman lasers fields. Finally, based on the measurements, I discuss a novel robust measurement technique involving interference of the Raman, M1 and E_PNC contributions.<br>

Apresentamos os resultados de medidas espectroscópicas feitas em átomos de elementos contidos em uma descarga elétrica do tipo catodo oco, usando um laser sintonizável de emissão contínua. Com experiências de absorção ótica foi possível determinar a densidade populacional e a temperatura dos átomos de 238U no estado fundamental, em função dos vários parâmetros que caracterizam a descarga. Desenvolvemos um método para a determinação da potência de saturação e calculamos o valor do produto para a transição 0 16.900cm-1 do 238UI. De forma alternativa às medidas óticas oudemos estudar a interação fóton-átomo analisando o sinal optogalvânico induzido na descarga pela radiação laser, com frequência sintonizada na mesma transição atômica do urânio e em função dos parâmetros anteriormente considerados. Os resultados obtidos com as experiências de absorção ótica e espectroscopia optogalvânica / The results of spectroscopic measurements obtained with atomic species present in a hollow cathode type discharge are reported. Using laser optical absorption techniques it was possible to get the population density and the atomic temperature of the 238UI ground state as a function of some discharge parameters. A method to determine the laser saturation intensity was developed, so the value of the product for the 0 16.900cm-1 238UI transition could be calculated. It was also possible to study the photon-atom interaction through the analysis of the optogalvanic signal induced in the laser radiation as a function of the same parameters considered before. Optogalvanic spectroscopy and optical absorption experiments showed the spatial distribution of the atoms in the ground state and excited states inside the cathode. In another set of experiments, a new way of inducing optogalvanic effect was investigated without using a tunable dye laser as the axcitation source. Measurements were done with two copper hollow cathode tubes filled with different gases, that were used as excitation source radiation and as signal detector. The results suggest that it is possible to use the new spectroscopy tecnique for qualitative and quantitative material analysis.

Apresentamos os resultados de medidas espectroscópicas feitas em átomos de elementos contidos em uma descarga elétrica do tipo catodo oco, usando um laser sintonizável de emissão contínua. Com experiências de absorção ótica foi possível determinar a densidade populacional e a temperatura dos átomos de 238U no estado fundamental, em função dos vários parâmetros que caracterizam a descarga. Desenvolvemos um método para a determinação da potência de saturação e calculamos o valor do produto para a transição 0 16.900cm-1 do 238UI. De forma alternativa às medidas óticas oudemos estudar a interação fóton-átomo analisando o sinal optogalvânico induzido na descarga pela radiação laser, com frequência sintonizada na mesma transição atômica do urânio e em função dos parâmetros anteriormente considerados. Os resultados obtidos com as experiências de absorção ótica e espectroscopia optogalvânica / The results of spectroscopic measurements obtained with atomic species present in a hollow cathode type discharge are reported. Using laser optical absorption techniques it was possible to get the population density and the atomic temperature of the 238UI ground state as a function of some discharge parameters. A method to determine the laser saturation intensity was developed, so the value of the product for the 0 16.900cm-1 238UI transition could be calculated. It was also possible to study the photon-atom interaction through the analysis of the optogalvanic signal induced in the laser radiation as a function of the same parameters considered before. Optogalvanic spectroscopy and optical absorption experiments showed the spatial distribution of the atoms in the ground state and excited states inside the cathode. In another set of experiments, a new way of inducing optogalvanic effect was investigated without using a tunable dye laser as the axcitation source. Measurements were done with two copper hollow cathode tubes filled with different gases, that were used as excitation source radiation and as signal detector. The results suggest that it is possible to use the new spectroscopy tecnique for qualitative and quantitative material analysis.