The aim of this study is to investigate the relation between venture capital and the number of high growth firms. Previous research has covered the relation at the firmlevel where the positive effect of venture capital on innovation, firm growth and economic growth has been established. However, the research field have been lacking a more aggregated approach. With a fixed effects panel regression with the number of high growth firms as the dependent variable and the amount of venture capital as the key independent variable, this study is conducted at the country-level with a panel of 20 countries. The study yield no significant results except the positive effect of GDP per capita. The conclusion is that the data available today is not ready for this level of aggregation as it captures to much noise with regards to other factors affecting firm growth in a country. Growth in employment might also be an outdated proxy to measure firm growth as today's modern firms are not as dependent on a large number of employees to scale as in the past. / Målet med denna studie är att undersöka relationen mellan riskkapital och snabbväxande företag. Tidigare studier har undersökt relationen på företagsnivå där riskkapitalets positiva effekt på innovation, firmatillväxt och ekonomisk tillväxt har påvisats. Dock har forskningsfältet saknat ett tillvägagångssätt på en mer aggregerad nivå. Med en fixed effects-modell applicerad på paneldata med en beroende variabel bestående av antalet snabbväxande företag och en oberoende variabel bestående av mängden riskkapital, undersöks relationen på landnivå med ett urval av 20 länder. Studien visar inga signifikanta resultat bortsätt från kontrollvariabeln BNP per capita som är positiv och signifikant. Slutsatsen i arbetet är att den data som finns tillgänglig idag inte är mogen för studier på en aggregerad landnivå då brus i form av andra faktorer som påverkar snabbväxande företag i ett land fångas upp. Företagstillväxt mätt i tillväxt i antalet anställda i ett företag kan även vara en föråldrad metod. Dagens moderna företag präglade av affärsmodeller som inte kväver arbetskraft för att skala upp verksamheten på samma sätt som företag traditionellt gjort historiskt.

In dieser Arbeit werden die Wechselwirkungen von Wasserstoff mit festen Materialien und Oberflächen untersucht. Zunächst wird der Kontext unserer Untersuchung durch eine kurze Einordnung in die Geschichte der Naturwissenschaften im Allgemeinen, und der Oberflächenforschung im Speziellen, hergestellt. Anschließend wird der quanten-mechanische Apparat, welcher nötig ist um die betrachteten Systeme zu beschreiben, eingeführt um dann detailliert die Potentialhyperfläche der Entstehung von Wasser durch Adsoprtion von Wasserstoff auf einer teilweise oxidierten Ruthenium(0001) Metalloberfläche zu studieren. Zudem wird das gleiche System betrachtet, wenn die Metalloberfläche zusätzlich von einer biatomaren, kristallinen Lage Siliziumdioxid (SiO2) bedeckt ist, wodurch eine räumliche Beengung eintritt. Wir verwenden unsere Ergebnisse zusammen mit experimentellen Beobachtungen und mathematischen Methoden um ein vollständig theoretisches Modell zu entwerfen und das System grundlegend verstehen zu können. In einem weiteren Schritt werden die chemischen Änderungen der Siliziumdioxid Doppellage untersucht, wenn das System Wasserstoffplasma ausgesetzt wird. Es werden diverse mögliche Defektstrukturen diskutiert und mithilfe experimenteller Befunde die wahrscheinlichste Struktur isoliert. Im letzten Kapitel werden die typischen Näherungen untersucht, welche notwendig sind um quantenmechanische Methoden mit Hilfe von Computern durchführbar zu machen. Wir verwenden den sogenannten embedded-fragment Ansatz um die Diffusionsbarriere von Wasserstoff auf Aluminiumoxid mit chemischer Genauigkeit zu berechnen. Unsere Ergebnisse auf dem coupled-cluster with singles, doubles and perturbative triples (CCSD(T))-Niveau können sowohl als Referenz für experimentelle Untersuchungen, als auch für andere quantenmechanische Methoden wie z.B. die Dichtefunktionaltheorie, angesehen werden. / The present thesis aims at investigating the interactions of hydrogen with solid surfaces and materials. We first offer a brief historical context for surface science, as well as quantum mechanics and science is general, before deriving the mathematical apparatus necessary to investigate our systems of interest. We then move on to explore the potential energy surface of the water-formation-reaction on a partially oxidized ruthenium(0001) surface when confined under a two-atom thick sheet of silica (SiO2). We further employ our findings in conjunction with experimental observations and mathematical modeling to set up a fully theoretical model of the system in order to explain its behavior. In the second chapter we investigate the chemical alteration of the ultra-thin silica bilayer by means of exposing it to hydrogen plasma. We elucidate possible defects formed during the process and pin-point the most likely structure found. In the last chapter, we investigate the possible error sources that are inherent in quantum mechanical modeling and employ the so called embedded fragment approach to lift the approximations up to the coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory. We then apply this methodology to the diffusion of hydrogen on aluminum oxide to obtain a diffusion barrier of chemical accuracy that may both be used to benchmark other approaches such as density functional theory, as well as experimental findings.

Die vorliegende Habilitationsschrift bespricht aktuelle Ergebnisse zur Struktur und Reaktivität von Übergangsmetalloxidoberflächen. Es werden eingangs Grundlagen zur Berechnung von Eigenschaften von Oberflächen mittels Dichtefunktionaltheorie vorgestellt. Des Weiteren werden anhand von drei untersuchten Oxiden, nämlich dem Vanadium(III)-oxid, dem Cer(IV)-oxid, und dem Eisen(II,III)-oxid, der aktuelle Forschungsstand im Hinblick auf Oberflächenstruktur und Reaktivität von Phasengrenzen, wie z.B. der Phasengrenze zwischen Vanadium(V)-oxid und Cer(IV)-oxid und der Phasengrenze zwischen Wasser und Eisen(II,III)-oxid dargelegt. / The present habilitation thesis discusses results on structure and reactivity of transition metal oxide surfaces obtained using state-of-the-art density functional theory methods. First, fundamental issues of density functional theory are presented. Furthermore, the current state in research with respect to surface structure on one hand and reactivities of interfaces between different oxides like vanadium(III) and cerium(IV) oxide or water and iron(II,III) oxide on the other hand are developed.

The South African economy, which is largely based on heavy industry such as minerals extraction and processing, is by nature very energy intensive. Based on the abundance of coal resources, electricity in South Africa remains amongst the cheapest in the world. Whilst the low electricity price has contributed towards a competitive position, it has also meant that our existing electricity supply is often taken for granted. The economic and environmental benefits of energy efficiency have been well documented. Worldwide, nations are beginning to face up to the challenge of sustainable energy - in other words to alter the way that energy is utilised so that social, environmental and economic aims of sustainable development are supported. South Africa as a developing nation recognises the need for energy efficiency, as it is the most cost effective way of meeting the demands of sustainable development. South Africa, with its unique economic, environmental and social challenges, stands to benefit the most from implementing energy efficiency practices. The Energy Efficiency Strategy for South Africa takes its mandate from the South African White Paper on Energy Policy. It is the first consolidated governmental effort geared towards energy efficiency practices throughout South Africa. The strategy allows for the immediate implementation of low-cost and no-cost interventions, as well as those higher-cost measures with short payback periods. An initial target has been set for an across sector energy efficiency improvement of 12% by 2014. Thermal and energy system simulation is globally recognised as one of the most effective and powerful tools to improve overall energy efficiency. However, because of the usual extreme mathematical nature of most simulation algorithms, coupled with the historically academic environment in which most simulation software is developed, valid perceptions exist that system simulation is too time consuming and cumbersome. It is also commonly known that system simulation is only effective in the hands of highly skilled operators, which are specialists in their prospective fields. Through previous work done in the field, and the design of a dynamic thermal and energy system simulation scheme for cross industry applications, it was shown that system simulation has evolved to such an extent that these perceptions are not valid any more. The South African mining and commercial building industries are two of the major consumers of electricity within South Africa. By improving energy efficiency practices within the building and mining industry, large savings can be realised. An extensive investigation of the literature showed that no general suitable computer simulation software for cross industry mining and building thermal and energy system simulation could be found. Because the heating, ventilation and air conditioning (HVAC) of buildings, closely relate to the ventilation and cooling systems of mines, valuable knowledge from this field was used to identify the requirements and specifications for the design of a new single cross industry dynamic integrated thermal and energy system simulation tool. VISUALQEC was designed and implemented to comply with the needs and requirements identified. A new explicit system component model and explicit system simulation engine, combined with a new improved simulation of mass flow through a system procedure, suggested a marked improvement on overall simulation stability, efficiency and speed. The commercial usability of the new simulation tool was verified for building applications by doing an extensive building energy savings audit. The new simulation tool was further verified by simulating the ventilation and cooling (VC) and underground pumping system of a typical South African gold mine. Initial results proved satisfactory but, more case studies to further verify the accuracy of the implemented cross industry thermal and energy system simulation tool are needed. Because of the stable nature of the new VISUALQEC simulation engine, the power of the simulation process can be further extended to the mathematical optimisation of various system variables. In conclusion, this study highlighted the need for new simulation procedures and system designs for the successful implementation and creation of a single dynamic thermal and energy system simulation tool for cross industry applications. South Africa should take full advantage of the power of thermal and energy system simulation towards creating a more energy efficient society. / Thesis (Ph.D. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2005.

The South African economy, which is largely based on heavy industry such as minerals extraction and processing, is by nature very energy intensive. Based on the abundance of coal resources, electricity in South Africa remains amongst the cheapest in the world. Whilst the low electricity price has contributed towards a competitive position, it has also meant that our existing electricity supply is often taken for granted. The economic and environmental benefits of energy efficiency have been well documented. Worldwide, nations are beginning to face up to the challenge of sustainable energy - in other words to alter the way that energy is utilised so that social, environmental and economic aims of sustainable development are supported. South Africa as a developing nation recognises the need for energy efficiency, as it is the most cost effective way of meeting the demands of sustainable development. South Africa, with its unique economic, environmental and social challenges, stands to benefit the most from implementing energy efficiency practices. The Energy Efficiency Strategy for South Africa takes its mandate from the South African White Paper on Energy Policy. It is the first consolidated governmental effort geared towards energy efficiency practices throughout South Africa. The strategy allows for the immediate implementation of low-cost and no-cost interventions, as well as those higher-cost measures with short payback periods. An initial target has been set for an across sector energy efficiency improvement of 12% by 2014. Thermal and energy system simulation is globally recognised as one of the most effective and powerful tools to improve overall energy efficiency. However, because of the usual extreme mathematical nature of most simulation algorithms, coupled with the historically academic environment in which most simulation software is developed, valid perceptions exist that system simulation is too time consuming and cumbersome. It is also commonly known that system simulation is only effective in the hands of highly skilled operators, which are specialists in their prospective fields. Through previous work done in the field, and the design of a dynamic thermal and energy system simulation scheme for cross industry applications, it was shown that system simulation has evolved to such an extent that these perceptions are not valid any more. The South African mining and commercial building industries are two of the major consumers of electricity within South Africa. By improving energy efficiency practices within the building and mining industry, large savings can be realised. An extensive investigation of the literature showed that no general suitable computer simulation software for cross industry mining and building thermal and energy system simulation could be found. Because the heating, ventilation and air conditioning (HVAC) of buildings, closely relate to the ventilation and cooling systems of mines, valuable knowledge from this field was used to identify the requirements and specifications for the design of a new single cross industry dynamic integrated thermal and energy system simulation tool. VISUALQEC was designed and implemented to comply with the needs and requirements identified. A new explicit system component model and explicit system simulation engine, combined with a new improved simulation of mass flow through a system procedure, suggested a marked improvement on overall simulation stability, efficiency and speed. The commercial usability of the new simulation tool was verified for building applications by doing an extensive building energy savings audit. The new simulation tool was further verified by simulating the ventilation and cooling (VC) and underground pumping system of a typical South African gold mine. Initial results proved satisfactory but, more case studies to further verify the accuracy of the implemented cross industry thermal and energy system simulation tool are needed. Because of the stable nature of the new VISUALQEC simulation engine, the power of the simulation process can be further extended to the mathematical optimisation of various system variables. In conclusion, this study highlighted the need for new simulation procedures and system designs for the successful implementation and creation of a single dynamic thermal and energy system simulation tool for cross industry applications. South Africa should take full advantage of the power of thermal and energy system simulation towards creating a more energy efficient society. / Thesis (Ph.D. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2005.

Even before the spread of COVID-19 video conferencing software has seen a steady rise in use. Due to their convenient way of offering a way of seeing the other participants live while talking to them, it is quite easy to see why this kind of software became more and more used throughout the years. Now, during the pandemic, video conferencing software is more used than ever before, especially in learning environments. Nevertheless, studies show that student engagement is rather low with university students who take part in online learning. Throughout this paper, we venture into discovering the reasons behind this lack of engagement and how it can be improved from a User Experience Design standpoint. With findings resulted from several previous studies and identified student problems and needs from those papers we created a prototype to test which features and design elements affected student engagement.

Awareness of vehicles’ surrounding conditions is important in today’s intelligent transportation system. A wide range of effort has been put in to deploy Vehicular Communication (VC) systems to make driving conditions safer and more efficient. Vehicles are aware of their surroundings with the help of authenticated safety beacons in VC systems. Since vehicles act according to the information conveyed by such beacons, verification of beacons plays an important role in becoming aware of and predicting the status of the sender vehicle. The idea of implementing secure mechanisms to deal with a high rate of incoming beacons and processing them with high efficiency becomes a very important part of the whole VC network. The goal of this work was to implement a scheme that deals with a high rate of the incoming beacon, preserve non-repudiation of the accepted messages which contains information about the current and near-future status of the sender vehicle, and at the same time keep the computation overhead as low as possible. Along with this, maintaining user privacy from a legal point of view as well as from a technical perspective by implementing privacy-enhancing technologies. These objectives were achieved by the introduction of Timed Efficient Stream Loss-Tolerant Authentication (TESLA), periodic signature verification, and cooperative verification respectively. Four different scenarios were implemented and evaluated, starting and building upon the baseline approach. Each approach addressed the problems that were aimed at this work and results show improved scalability and efficiency with the introduction of TESLA, periodic signature verification, and cooperative verification. / Medvetenheten om fordons omgivande förhållanden är viktig i dagens intelligenta transportsystem. Ett stort antal ansträngningar har lagts ned för att distribuera VC system för att göra körförhållandena säkrare och effektivare. Fordon är medvetna om sin omgivning med hjälp av autentiserade säkerhetsfyrar i VC system. Eftersom fordon agerar enligt den information som förmedlas av sådana fyrar, spelar verifiering av fyrar en viktig roll för att bli medveten om och förutsäga avsändarfordonets status. Idén att implementera säkra mekanismer för att hantera en hög frekvens av inkommande fyrar och bearbeta dem med hög effektivitet blir en mycket viktig del av hela VC nätverket. Målet med detta arbete var att implementera ett schema som behandlar en hög hastighet för det inkommande fyren, bevara icke-förkastelse av de accepterade meddelandena som innehåller information om den aktuella och närmaste framtida statusen för avsändarfordonet och samtidigt håll beräkningen så låg som möjligt. Tillsammans med detta upprätthåller användarnas integritet ur juridisk synvinkel såväl som ur ett tekniskt perspektiv genom att implementera integritetsförbättrande teknik. Dessa mål uppnåddes genom införandet av TESLA, periodisk signatur verifiering respektive samarbets verifiering. Fyra olika scenarier implementerades och utvärderades med utgångspunkt från baslinjemetoden. Varje tillvägagångssätt tog upp de problem som riktades mot detta arbete och resultaten visar förbättrad skalbarhet och effektivitet med införandet av TESLA, periodisk signatur verifiering och samarbets verifiering.

Ein fragment-basierter Ansatz zur Berechnung von vertikalen Anregungsenergien in periodischen Systemen wurde entwickelt. Das Ziel war eine wellenfunktions-basierte Hierarchie von lokalen post-Hartree-Fock Methoden, welche über das weitverbreitete Ein-Elektronen Bild der Bandlücke hinausgehen und eine Möglichkeit zur systematischen Verbesserung der Ergebnisse liefern. Darüber hinaus sollte durch die Verwendung von lokalen Orbitalen eine nahtlose Einbettung des Fragments ermöglicht und eine effektive Methode für die Untersuchung von Defekten in periodischen Systemen geschaffen werden. Als erster Schritt wird das fragment-basierte Configuration Interaction Singles (CIS) Model vorgestellt. Im Anschluss erfolgt der Wechsel zum fragment-basierten lokalen algebraic-diagrammatic construction Modells zweiter Ordnung (DF-LADC(2)). Beide Methoden wurden für ein neutrales Farbzentrum in Magnesiumoxid (MgO) getestet. Dabei wurden Fragmente mit bis zu 57 Atomen verwendet. Eine Konvergenz mit der Fragmentgröße, der Größe der Superzellen und des K-mesh konnte erreicht werden. Dennoch wurde eine erste Anregungsenergie von 5.9 eV erhalten, was 0.9 eV über dem veröffentlichten experimentellen Wert liegt. Mit hoher Wahrscheinlichkeit rührt die Abweichung vom Basissatzvollständigkeitsfehler her. ”Finite-Cluster”-Berechnungen bestätigen entsprechende Basissatzfehler. Interessanterweise stimmt die erste Anregungsenergie für ein Oberflächenfarbzentrum in MgO mit einigen experimentellen Werten überein. Allerdings decken die experimentellen Werte für diese Systeme einen weiten Bereich ab (1.15 - 4.2 eV). / An embedded-fragment approach for calculation of vertical excitation energies in periodic systems has been developed. The aim is a wave-function-based hierarchy of local post-Hartree-Fock models, which goes beyond the very common one-electron picture of the band gap and offers a way for systematic improvability of the results. The use of local occupied and virtual orbitals allows for a seamless embedding model for the fragment and becomes especially effective in studying defects in solids. As a first step in the hierarchy an embedded-fragment Configuration Interaction Singles (CIS) model is presented. The second step is an embedded-fragment local algebraic diagrammatic construction scheme of second order (DF-LADC(2)). Both methods are tested for an neutral color center in bulk and surface magnesium oxide (MgO). Different fragments with up to 57 atoms were studied. A convergence with fragment size, super-cell size and k-mesh has been achieved. However a first excitation energy of 5.9 eV is obtained for the bulk MgO, which is 0.9 eV above the reported experimental value. The deviation most likely originates from the basis set incompleteness error, which, according to finite cluster studies, can be sizable. Interestingly for a surface color center in MgO the observed first excitation energy of 4.1 eV agrees with some of the experimental values (4.2 eV). However for the surface color centers in MgO the scatter of the experimental results is very large (1.15 eV - 4.2 eV).

In dieser Arbeit wird eine unrestricted Coupled-Cluster CC2 Response-Methode für die Berechnung von Eigenschaften erster und zweiter Ordnung, mit dem elektronischen g-Tensor als Schwerpunkt, präsentiert. Lokale Korrelations- und Dichtefittingnäherungen wurden verwendet. Die fundamentalen Konzepte notwendig für das Verständnis von Coupled-Cluster-Theorie, Dichtefitting, lokaler Korrelation, allgemeinen Coupled-Cluster Eigenschaften und dem elektronischen g-Tensor werden diskutiert. Die berechneten g-Tensoren werden mit denen durch Coupled-Cluster Singles and Doubles, Dichtefunktionaltheorie und Experiment erhaltenen verglichen. Effizienz und Genauigkeit der Näherung wird untersucht. Ein detailierter Anhang beschreibt die diagrammatische Coupled-Cluster-Theorie sowie ihre Anwendung zur Herleitung der verwendeten Arbeitsgleichungen. Die in dieser Arbeit entwickelte Methode ermöglicht es, den elektronischen g-Tensor von ausgedehnten Systemen mit einer Methode, die nicht auf Dichtefunktionaltheorie basiert, quantitativ vorherzusagen. Damit ist sie ein wichtiger Schritt hin zur Entwicklung von niedrig skalierenden Coupled-Cluster-Methoden höherer Ordnung für diese Art von Problem. / This work presents an unrestricted coupled-cluster CC2 response method using local correlation and density fitting approximations for the calculation of first and second order properties with particular focus on the electronic g-tensor. The fundamental concepts related to coupled-cluster theory, density fitting, local correlation, general coupled-cluster properties and the electronic g-tensor are discussed. The calculated g-tensors are benchmarked against those obtained from coupled-cluster singles and doubles, density functional theory and experiment. Efficiency and accuracy of the approximations is investigated. A detailed appendix covers the fundamentals of diagrammatic coupled-cluster and its application to the derivation of the working equations. The method presented in this thesis enables the quantitative prediction of the electronic g-tensor of extended systems with a method other than density functional theory. It represents an important step towards the development of low-scaling higher order coupled-cluster methods for this type of problem.

Ziel dieser Arbeit war die Entwicklung einer allgemein anwendbaren Methode für die Simulation von ultraschnellen Prozessen und experimentellen Observablen. Hierfür wurden die Berechnung der elektronischen Struktur mit der zeitabhängigen Dichtefunktionaltheorie (TDDFT) und das Tully-Surface-Hopping-Verfahren für die nichtadiabatische Kerndynamik auf der Basis klassischer Trajektorien miteinander kombiniert. Insbesondere wurde eine Beschreibung der nichtadiabatischen Kopplungen für TDDFT entwickelt. Diese Methode wurde für die Simulation noch komplexerer Systeme durch die Tight-Binding-Näherung für TDDFT erweitert. Da die zeitaufgelöste Photoelektronenspektroskopie (TRPES) ein exzellentes experimentelles Verfahren für die Echtzeitbeobachtung von ultraschnellen Prozessen darstellt, wurde eine TDDFT-basierte Methode für die Simulation von TRPES entwickelt. Der Methode liegt die Idee zu Grunde, das System aus Kation und Photoelektron näherungsweise durch angeregte Zustände des neutralen Moleküls oberhalb der Ionisierungsgrenze zu beschreiben. Um diese Zustände mit TDDFT berechnen zu können wurde eine Beschreibung der Übergangsdipolmomente zwischen angeregten TDDFT-Zuständen entwickelt. Des Weiteren wurden Simulationen im Rahmen des Stieltjes-Imaging-Verfahrens, das eine Möglichkeit der Rekonstruktion des Photoelektronenspektrums aus den spektralen Momenten bietet, durchgeführt. Diese spektralen Momente wurden aus den diskreten TDDFT-Zuständen berechnet. Die breite Anwendbarkeit der entwickelten theoretischen Methoden für die Simulation von komplexen Systemen wurde an der Photoisomerisierung in Benzylidenanilin sowie der ultraschnellen Photodynamik in Furan, Pyrazin und mikrosolvatisiertem Adenin illustriert. Die dargestellten Beispiele demonstrieren, dass die nichtadiabatische Dynamik im Rahmen von TDDFT bzw. TDDFTB sehr gut für die Untersuchung und Interpretation der ultraschnellen photoinduzierten Prozesse in komplexen Molekülen geeignet ist. / The goal of this thesis was the development of a generally applicable theoretical framework for the simulation of ultrafast processes and experimental observables in complex molecular systems. For this purpose, a combination of the time-dependent density functional theory (TDDFT) for the description of the electronic structure with the Tully''s surface hopping procedure for the treatment of nonadiabatic nuclear dynamics based on classical trajectories was employed. In particular, a new approach for the calculation of nonadiabatic couplings within TDDFT was devised. The method was advanced for the description of more complex systems such as chromophores in a solvation shell by employing the tight binding approximation to TDDFT. Since the time-resolved photoelectron spectroscopy (TRPES) represents a powerful experimental technique for real-time observation of ultrafast processes, a TDDFT based approach for the simulation of TRPES was developed. The basic idea is the approximate representation of the combined system of cation and photoelectron by excited states of the neutral species above the ionization threshold. In order to calculate these states with TDDFT, a formulation of the transition dipole moments between excited states within TDDFT was devised. Moreover, simulations employing the Stieltjes imaging (SI) procedure were carried out providing the possibility to reconstruct photoelectron spectra from spectral moments. In this work, the spectral moments were calculated from discrete TDDFT states. The scope of the developed theoretical methods was illustrated on the photoisomerization in benzylideneaniline as well as on the ultrafast photodynamics in furan, pyrazine, and microsolvated adenine. The examples demonstrate that the nonadiabatic dynamics simulations based on TDDFT and TDDFTB are particularly suitable for the investigation and interpretation of ultrafast photoinduced processes in complex molecules.