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Thesis (MSc)--Stellenbosch University, 2012. / AFRIKAANSE OPSOMMING: Berekeninge met Density Functional Theory (DFT) is ’n nuttige tegniek om die dinamika van molekules op potensiële energievlakke te verstaan. Beginnende met ’n prototipe molekuul formaldimien, wat die kern vorm van die groter fotochromiese molekuul dithizonatophenyl kwik (DPM), word die modellering van die molekuul meer ingewikkeld tot laasgenoemde bestudeer kan word asook sy fotochromiese afgeleides wat vervanging van elektronryk en elektronarm radikale by orto, meta en para posisies van die phenyl ringe insluit. DFT berekeninge word met spektra van Absorpsiespektroskopie met UV en sigbare lig asook tyd opgeloste spektra, verkry dmv femtosekondespektroskopie, vergelyk. In pol^ere aprotiese, pol^ere protiese en nie-pol^ere oplosmiddels, isomeriseer die molekuul om die C=N dubbelbinding. Daar kan tussen die twee isomere onderskei word deur dat die een in oplossing in sy grondtoestand blou en die ander een oranje voorkom. Die isomerisering is’n fotogeinduseerde proses. Die optimering van die molekul^ere struktuur, absorpsiespektra, oplosmiddel-afhanklikheid, en potensiële energievlak metings van die molekuul word bestudeer. Die sterk/swak wisselwerking wat in pol^ere protiese/aprotiese oplosmiddels verskyn word geopenbaar deur die hoe/lae absorpsie van die sekond^ere bande van die molekules. Daar is gevind dat die absorpsiespektra van DPM bathochromies in oplosmiddels met hoë diëlektriese konstantes is. Vir die potensiële energievlak berekeninge van die grondtoestand word rigiede en ontspanne metodes gebruik waar laasgenoemde met gebroke simmetrie berekeninge verkry word. Van alle metodes wat vir berekeninge gebruik was, gee die B3LYP/CEP-31G metode die beste benadering aan eksperimentele data. Alle berekeninge word gedoen met twee bekende sagteware pakkette; Amsterdam Density Functional (ADF) en Gaussian, wat op twee verskillende DFT metodes gebaseer is. / ENGLISH ABSTRACT: Density functional theory is a useful computational tool in the understanding of molecular dynamics on potential energy surfaces. Starting with a prototype molecule formaldimine, the photochromic molecule dithizonatophenylmercury II (DPM) and a set of its photochromic derivatives, (involving substitutions of electron donating and electron withdrawing substituents at ortho, meta and para positions of the dithizonato phenyl rings), are studied through density functional calculation in comparison with steady state absorption spectra obtained from UV-Visible and femto second spectroscopy experiments. In polar aprotic, polar protic and non-polar solvents these molecules isomerise around C=N double bond chromophore, from orange electronic ground states to blue electronic ground states upon photo-excitation. We investigate the structural optimisations, the absorption spectra, the solvent dependence and the potential energy surface (PES) of these molecules. The strong (weak) interactions exhibited by the polar protic (aprotic) solvents used are revealed through high (low) absorbance in the secondary bands of these molecules. The absorption spectra of DPM are found to be bathochromic in solvents with high dielectric constants. For the ground state PES calculation we make use of rigid and relaxed methods, and the latter is obtained through broken symmetry calculation. Of all the methods used in calculation, B3LYP/CEP-31G method gives the best approximation to the experimental data. All calculations are done using the two renown software, Amsterdam Density Functional (ADF) and Gaussian, availing their different density functional methods.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Trilayered transition metal dichalcogenides such as our sample (1T-TiSe2) have been studied for many years as systems with strong electron-electron and electron-phonon correlations. The main attraction to this family of compound is its potential to exhibit ground state phenomena known as charge density waves whose detailed physical origin has been controversially determined. In this study, we have used an ultrafast femtosecond laser based on a pump-probe technique, namely ultrafast electron diffraction, to investigate these exotic features associated with the crystal. A pump laser pulse photo-excites the crystal from its ground state and the probe pulse (ultrashort electron pulse) takes the snapshot of the evolution of the lattice generating an electron diffraction pattern of the crystal. Hence the dynamical structural behaviour can be observed in time with a subpicosecond temporal resolution. As a hexagonal close-packed structure, its signature is expected to be seen in the diffraction pattern in both a steady-state and electron time-resolved femtosecond electron diffraction. In addition, simulations of electron diffractions pattern for room and low temperature structural data via a software called Simulation and Analysis of Electron diffraction (SAED) have been carried out. Clear signatures of charge density waves were seen at low temperature. / AFRIKAANSE OPSOMMING: Drie-laag oorgangsmetaal dikhalkogeniedes soos ons voorbeeld (1T-TiSe2), word reeds vir baie jare bestudeer as sisteme met sterk elektron-elektron en elektron-fonon korrelasies. Die hoof aantrekkingskrag van hierdie sisteme is die verskynsel van ladingdigtheidsgolwe in die grondtoestand. Die fisiese oorsprong van hierdie ladingdigtheidsgolwe was bepaal te midde van verskeie teenstrydighede. In hierdie studie, maak ons gebruik van die ultravinnige femtosekonde laser gebaseerde aktiveer-interogeer tegniek, genaamd ultravinnige elektron diffraksie (UED) om unicke eienskappe wat met die kristal geassosieer is te bestudeer. In UED wek ’n ultravinnige laserpuls (aktivering) die kristal op vanaf die grondtoestand waartydens n ultravinnige elektronpuls (interogering) ’n foto neem van die evolusie van die elektron diffraksiepatroon wat deur die kristalrooster gegenereer word. Hierdie wisselwerking van die interogerings elektronpuls en die sisteem kan gevolglik teen verskeie vasgetelde tye toegelaat word. Dus kan die dinamiese strukturele gedrag waargeneem word met ’n tydresolusie in die orde van die elektronpuls (sub-pikosekondes). Siende dat die kristal ’n diggepakte-heksagonale struktuur vorm, behoort die kenmerkende diffraksiepatroon daarvan waarneembaar te wees in beide die bestendige diffraksie en femtosekonde elektron diffraksie tegnieke. In hierdie konteks was duidelike tekens van ladingdigtheidsgolwe waargeneem. Benewens was daar ook simulasies uitgevoer om die elektron diffraksiepatrone asook die strukturele data by kamer en lae temperature vas te pen. Die sagteware wat hiervoor gebruik word is genaamd Simulasie en Ontleding van Elektronendiffraksie (SAED) - Simulation and Analysis of Electron Diffraction (SAED).

With increasing global energy demand and diminishing fossil fuel supplies, the development of clean and affordable renewable energy technology is more important than ever. Photovoltaic devices harvest the sun’s energy to produce electricity and produce very little pollution compared to nonrenewable sources. In order to make these devices affordable, however, technological advances are required. In this dissertation a novel photovoltaic device architecture that is designed to enhance sunlight-to-electricity conversion efficiency of photovoltaics is proposed and demonstrated. The increase in efficiency arises due to enhancement of the internal quantum efficiency of photoexcitation in the semiconductor absorber. In other words, the probability that the absorption of a single photon will produce two or more electron-hole pairs, instead of just one, is increased. This occurs through the process of impact ionization, by which a highly excited charge carrier (via absorption of a high energy photon) relaxes by excitation of a second electron-hole pair. The result is an increased photocurrent, and efficiency, of the photovoltaic device. Using thin films of ZnS on Si substrates, we demonstrate that the probability of impact ionization is enhanced at the (unbiased) heterojunction between these layers. The magnitude of enhancement depends on material properties, including crystallinity of the ZnS film as well as concentration of oxygen (impurity) at the interface. Thin films of ZnSe on Si substrates do not exhibit heterojunction-assisted impact ionization, but they do display promising characteristics that make them an intriguing system for future work. The same is true for ZnS/Si materials fabricated by O2-free chemical bath deposition. For the analysis of plain Si as well as ZnS/Si and ZnSe/Si heterostructures, we employ a novel pump-probe transient transmission and reflection spectroscopy technique. A method is demonstrated for using this technique to quantify internal quantum efficiency as well as interface recombination velocity in each of these materials. In bulk silicon, a free carrier absorption cross section that depends on free carrier concentration (above 1018 cm-3) is observed and the relationship is quantified. This dissertation includes unpublished and previously published co-authored material.

The biological significance of photosynthesis is indisputable as it is necessary for nearly all life on earth. Photosynthesis provides chemical energy for plants, algae, and bacteria, while heterotrophic organisms rely on these species as their ultimate food source. The initial step in photosynthesis requires the absorption of sunlight to create electronic excitations. Light-harvesting proteins play the functional role of capturing solar radiation and transferring the resulting excitation to the reaction centers where it is used to carry out the chemical reactions of photosynthesis. Despite the wide variety of light-harvesting protein structures and arrangements, most light-harvesting proteins are able to utilize the captured solar energy for charge separation with near perfect quantum efficiency. This thesis will focus on understanding the energy transfer dynamics and photophysics of a specific subset of light-harvesting antennae known as phycobiliproteins. These proteins are extracted from cryptophyte algae and are investigated using steady-state and ultrafast spectroscopic techniques.

The biological significance of photosynthesis is indisputable as it is necessary for nearly all life on earth. Photosynthesis provides chemical energy for plants, algae, and bacteria, while heterotrophic organisms rely on these species as their ultimate food source. The initial step in photosynthesis requires the absorption of sunlight to create electronic excitations. Light-harvesting proteins play the functional role of capturing solar radiation and transferring the resulting excitation to the reaction centers where it is used to carry out the chemical reactions of photosynthesis. Despite the wide variety of light-harvesting protein structures and arrangements, most light-harvesting proteins are able to utilize the captured solar energy for charge separation with near perfect quantum efficiency. This thesis will focus on understanding the energy transfer dynamics and photophysics of a specific subset of light-harvesting antennae known as phycobiliproteins. These proteins are extracted from cryptophyte algae and are investigated using steady-state and ultrafast spectroscopic techniques.

This thesis deals with infrared studies of impurity states, ultrafast carrier dynamics as well as coherent intersubband polarizations in semiconductor quantum structures such as quantum wells and superlattices, based on the GaAs/AlGaAs material system. In the first part it is shown that the 2pz confined impurity state of a semiconductor quantum well develops into an excited impurity band in the case of a superlattice. This is studied by following theoretically the transition from a single to a multiple quantum well or superlattice by exactly diagonalizing the three-dimensional Hamiltonian for a quantum well system with random impurities. Intersubband absorption experiments, which can be nearly perfectly reproduced by the theory, corroborate this interpretation, showing that at low temperatures in the low doping density regime all optical transitions originate from impurity transitions. These results also require reinterpretation of previous experimental data. The relaxation dynamics of interminiband transitions in doped GaAs/AlGaAs superlattices in the mid-IR are studied. This involves single-color pump-probe measurements to explore the dynamics at different wavelengths, which is performed with the Rossendorf freeelectron laser (FEL), providing picosecond pulses in a range from 3-200 µm and are used for the first time within this thesis. In these experiments, a fast bleaching of the interminiband transition is observed followed by thermalization and subsequent relaxation, whose time constants are determined to be 1-2 picoseconds. This is followed by an additional component due to carrier cooling in the lower miniband. In the second part, two-color pump-probe measurements are performed, involving the FEL as the pump source and a table-top broad-band tunable THz source for probing the transmission changes. These measurements allow a separate specification of the cooling times after a strong excitation, exhibiting time constants from 230 ps to 3 ps for different excitation densities and miniband widths. In addition, the dynamics of excited electrons within the minibands is explored and their contribution quantitatively extracted from the measurements. Intersubband absorption experiments of photoexcited carriers in single quantum well structures, measured directly in the time-domain, i.e. probing coherently the polarization between the first and the second subband, are presented. From the data we can directly extract the density and temperature dependence of the intersubband dephasing time between the two lowest subbands, ranging from 50 up to 400 fs. This all optical approach gives us the ability to tune the carrier concentration over an extremely wide range which is not accessible in a doped quantum well sample. By varying the carrier density, many-body effects such as the depolarization and their influence on the spectral position as well as on the lineshape on the intersubband dephasing are studied. Also the difference of excitonic and free-carrier type excitation is discussed, and indication of an excitonic intersubband transition is found.

The scientific relevance and potential for technological applications of complex materials have made them the focus of active investigation in order to fully charac- terize the competition and interactions between their electronic, structural, orbital, and spin degrees of freedom. Optical and terahertz (THz) spectroscopy provide ac- cess to electronic and low frequency quasiparticle responses, and therefore play a key role in understanding the fundamental mechanisms which dictate the macroscopic properties of complex materials. Time-resolved experiments, in turn, have the po- tential to disentangle the various coexisting energy scales through a careful selection of the pump and probe characteristics. This work investigates the role played by the electronic, structural and magnetic excitations in the insulator-to-metal transi- tions (IMT) of VO2, V2O3 and NdNiO3, through studies under different conditions of temperature, strain, doping and photoexcitation. Our work shows that a complete understanding of the IMT in VO2 requires sev- eral length scales and time scales to be considered. Indeed, epitaxial strain leads to anisotropy in the IMT characteristics of thin films of (100) and (110) VO2/TiO2, measured using THz spectroscopy, which can be explained by strain induced modi- fications both in the (microscopic) V3d orbitals and in the geometry of mesoscopic metallic domains. On the other hand, ultrafast studies which track, with femtosecond resolution, the electronic and structural dynamics of VO2 thin films following THz excitation reveal a delay in the onset of the structural response with respect to the electronic one, lending support to the correlation rather than Peierls driven picture of the IMT in this material. As for V2O3, the IMT is seen to occur via nucleation and growth of metallic domains, as previously reported in VO2. However, a scaling of the photoinduced conductivity dynamics rise time is further identified, which reveals the temperature and fluence dependence of the nucleation and growth process. Finally, strained NdNiO3 films exhibit a two step dynamical conductivity response following optical excitation, different from that of the vanadates with which they share a complex, albeit more tunable, phase diagram. This hints at a significant role being played by the magnetic structure during the IMT in NdNiO3.

ROLE ASOVÉ 'KÁLY INTERAKCE SYSTÉM-LÁZE VE FOTOSYNTETICKÉM P ENOSU EXCITANÍ ENERGIE Tato práce se věnuje vlivu rychlého a pomalého molekulárno pohybu na přenos excitační energie ve fotosyntetick- ých světlosběrných komplexech. Vyvinuli jsme nový teoretický popis vnitromolekulárních vibračních mod· a zjistili jsme, že jejich resonance s energetickými rozdíly mezi fotosyntetickými pigmenty m·že vést ke zrychlení přenosu energie. Použitím jednomolekulární spektroskopie jsme pozorovali jak pomalé změny bílkovinné konformace mohou zcela změnit stav světlosběrného komplexu LHCII vyšších rostlin. Také jsme vyvinuli novou experimentální techniku, dvoupulzní ultrarychlou jednomolekulární spektroskopii. S její pomocí m·žeme pozorovat jak pomalý pohyb bílkoviny bakteriální antény LH2 ovlivňuje ultrarychlou relaxaci energie uvnitř komplexu. Konstrukcí jednotného modelu pro ultrarychlé objemové a jednomolekulární experimenty se nám podařilo zakomponovat rychlou a pomalou časovou škálu molekulárního pohybu do jednoho pohledu na fotosyntetický sběr světla.