Cálculos usando métodos de estrutura eletrônica (Hartree-Fock, Mõller-Plesset de segunda ordem e DFT, B3LYP) foram efetuados pelo programa Gaussian98 em microcomputadores e estações de trabalho, com o objetivo de elucidar os canais de decomposição unimolecular de éter dietílico em fase gasosa e foram comparados com valores obtidos através de aproximações baseadas na mecânica estatística pela metodologia de Benson. O éter dietílico vem sendo usado como um aditivo para o óleo diesel e combustível alternativo e o conhecimento de suas vias vias de decomposição é fundamental nestas investigações. Dezesseis modos primários, do qual, quatro ocorrem através de cisão de ligações simples C-O, C-C,C(1)-H e C(2)-H e doze ocorrendo através de estados de transição cíclicos, os quais eliminam produtos como hidrogênio etano, acetaldeído, etano, álcool etílico, metil etil éter, metano, alguns carbenos e também di-radicais, foram considerados para a determinação das barreiras de ativação, entalpias de reação, entropias de reação e energia livre de Gibbs de reação. Vias primárias ocorrendo através de cisão de ligação, não reproduziram os valores experimentais para as barreiras de ativação, mas reproduziram de modo significante, valores da entalpia da reação. Eliminação de eteno e álcool etílico, ocorrendo através de um estado de transição de quatro centros, apresentou a barreira de ativação mais baixa. Acetaldeído e eliminação de etano, ocorrendo através de quatro centros, apresentou barreira significativamente alta, mas por outro lado, a menor entalpia, ligeiramente exotérmica por -0,8 kcal.mol-1. Eliminações 1,2 de metano e carbeno ocorrendo através de três centros, junto com a eliminação 1, 1 de hidrogênio e carbeno por três centros, eliminação 2,2 hidrogênio e carbeno por três centros e eliminação 1,4 de hidrogênio, acetaldeído e eteno por seis centros, apresentaram barreiras de ativação relativamente próximas mostrando que elas são competitivas entre si. Os valores computados dos canais que ocorrem por estados de transição cíclicos foram comparados com os resultados experimentais disponíveis e discutida a validade desta abordagem computacional para o estudo de reações unimoleculares de multi-canais. Determinação de parâmetros termoquímicos, como calor de formação para espécies radicalares dos canais de decomposição primário e alguns radicais alcóxidos, junto com a estimativa de afinidade eletrônica e protônica (com a abordagem ab initio Gaussian 2 a qual estima energias eletrônicas muito precisas) foram efetuados e seus resultados foram comparados com os valores experimentais disponíveis e valores obtidos através de energias de ligação e da regra de aditividade de Benson. / Calculations using methods of electronic structure(Hartree-Fock, second order Moller-Plesset and DFT: B3LYP) had been effected through the Gaussian98 program in microcomputers and workstations, with the objective to elucidate the unimolecular decomposition channels of diethyl ether in gaseous phase. These results also had been compared to those obtained by the methodology based in statistical mechanics through Benson\'s approach. Sixteen primary ways, which, four occur through the break of simple bonds C-O, C-C,C(1)-H, C(2)-H, and twelve occur through cyclical transistion states, which eliminate products as hydrogen, ethene, acetaldehyde, ethane, ethyl alcohol, methyl ethyl ether, methane, some carbenes and also diradicals. These products had been considered to the determination of the activation barriers, enthalpies of reaction, entropies of reaction and free energy of Gibbs of reaction. Primary ways occurring through the break of bonds, had not reproduced experimental values for the activation barriers, however they had reproduced in a significant way, values of the enthalpy of the reaction. Elimination of ethene and ethyl alcohol, occurring by a transition state of four centers, presented the lowest activation barrier. Acetaldehyde and ethane elimination occurring through four centers, presented a high significantly barrier, but on the other hand it presented the smallest enthalpy, lightly exothermic above -0,8 kcal.mol-1. Eliminations 1,2 of methane and carbene occurring through three centers, together with the elimination 1,1 of hydrogen and carbene through three centers, elimination 2,2 of hydrogen and carbene through three centers and elimination 1,4 of hydrogen, acetaldehyde and ethene through six centers, had presented relatively next activation barriers, showing that they are competitive among themselves. The computed values of the channels that occur through cyclical transition states had been compared with the available experimental results and the trustworthiness of this computational boarding for the study of unimolecular reactions in multi-channel had been dicussed. Determination of thermochemical parameters, as heat of formation for radicalar species of the primary channel of decomposition and some alcoxyde radicais, together with the estimative of the electronic and protonic affinities,( with the ab initio Gaussian 2 boarding which estimate very precise eletronic energies ) and their results had been compared with the available experimental values and with values gotten through energies of bond and Benson\'s additivity rule.

In der vorliegenden Diplomarbeit wurden sekundäre Isotopeneffekte auf NMR-chemische Verschiebungen mit ab-initio quantenchemischen Methoden bestimmt. Um die zu erwartenden Fehler verschiedener Methoden abschätzen zu können, wurden die sekundären Isotopeneffekte von Fluor(2-2H1)ethan auf HF, MP2 und CCSD(T)-Niveau mit tripel- und quadrupel-Zeta Basissätzen berechnet. Anhand der Ergebnisse dieser Rechnungen lässt sich zeigen, dass gauche und antiperiplanare Konformere bereits mithilfe von sekundären Isotopenverschiebungen unterschieden werden können, die auf HF/tz2p-Niveau berechnet wurden. Weiterhin wurde untersucht, ob es eine Abhängingkeit des Isotopeneffektes von den Diederwinkeln zwischen Deuterium- und Fluorsubstituenten gibt. Die sekundären Isotopeneffekte auf 19F-NMR-chemische Verschiebungen von exo- und endo-2-Fluornorbornanen mit Deuterium Substituenten in den endo-3, exo-3, syn-7 oder anti-7 Positionen wurden auf HF/tz2p-Niveau berechnet. Es wird gezeigt, dass die berechneten Isotopeneffekte an 2-Fluornorbornanen eine Identifizierung der verschiedenen Stereoisomere erlauben. / In the present Diploma thesis secondary isotope effects on NMR chemical shieldings were determined using ab-initio quantum chemical methods. In order to estimate errors of various methods, secondary isotope effects on fluoro(2-2H1)ethane were calculated at the HF, MP2 and CCSD(T) level of theory using triple- and quadruple zeta basis sets. On the basis of these calculations it can be shown that gauche and antiperiplanar conformers can already be distinguished by their secondary isotope shifts calculated at the HF/tz2p level of theory. Furthermore it was investigated, whether a dependency of the isotope effects on dihedral angles between the deuterium and the fluorine substituent exists. The secondary isotope effects on 19F chemical shifts of exo- and endo-2-fluoronorbornanes with deuterium subsituents in the endo-3, exo-3, syn-7 or anti-7 positions were calculated at the HF/tz2p level. It is shown that the calculated isotope effects of 2-fluoronorbornanes allow to identify various stereoisomers.

Cálculos usando métodos de estrutura eletrônica (Hartree-Fock, Mõller-Plesset de segunda ordem e DFT, B3LYP) foram efetuados pelo programa Gaussian98 em microcomputadores e estações de trabalho, com o objetivo de elucidar os canais de decomposição unimolecular de éter dietílico em fase gasosa e foram comparados com valores obtidos através de aproximações baseadas na mecânica estatística pela metodologia de Benson. O éter dietílico vem sendo usado como um aditivo para o óleo diesel e combustível alternativo e o conhecimento de suas vias vias de decomposição é fundamental nestas investigações. Dezesseis modos primários, do qual, quatro ocorrem através de cisão de ligações simples C-O, C-C,C(1)-H e C(2)-H e doze ocorrendo através de estados de transição cíclicos, os quais eliminam produtos como hidrogênio etano, acetaldeído, etano, álcool etílico, metil etil éter, metano, alguns carbenos e também di-radicais, foram considerados para a determinação das barreiras de ativação, entalpias de reação, entropias de reação e energia livre de Gibbs de reação. Vias primárias ocorrendo através de cisão de ligação, não reproduziram os valores experimentais para as barreiras de ativação, mas reproduziram de modo significante, valores da entalpia da reação. Eliminação de eteno e álcool etílico, ocorrendo através de um estado de transição de quatro centros, apresentou a barreira de ativação mais baixa. Acetaldeído e eliminação de etano, ocorrendo através de quatro centros, apresentou barreira significativamente alta, mas por outro lado, a menor entalpia, ligeiramente exotérmica por -0,8 kcal.mol-1. Eliminações 1,2 de metano e carbeno ocorrendo através de três centros, junto com a eliminação 1, 1 de hidrogênio e carbeno por três centros, eliminação 2,2 hidrogênio e carbeno por três centros e eliminação 1,4 de hidrogênio, acetaldeído e eteno por seis centros, apresentaram barreiras de ativação relativamente próximas mostrando que elas são competitivas entre si. Os valores computados dos canais que ocorrem por estados de transição cíclicos foram comparados com os resultados experimentais disponíveis e discutida a validade desta abordagem computacional para o estudo de reações unimoleculares de multi-canais. Determinação de parâmetros termoquímicos, como calor de formação para espécies radicalares dos canais de decomposição primário e alguns radicais alcóxidos, junto com a estimativa de afinidade eletrônica e protônica (com a abordagem ab initio Gaussian 2 a qual estima energias eletrônicas muito precisas) foram efetuados e seus resultados foram comparados com os valores experimentais disponíveis e valores obtidos através de energias de ligação e da regra de aditividade de Benson. / Calculations using methods of electronic structure(Hartree-Fock, second order Moller-Plesset and DFT: B3LYP) had been effected through the Gaussian98 program in microcomputers and workstations, with the objective to elucidate the unimolecular decomposition channels of diethyl ether in gaseous phase. These results also had been compared to those obtained by the methodology based in statistical mechanics through Benson\'s approach. Sixteen primary ways, which, four occur through the break of simple bonds C-O, C-C,C(1)-H, C(2)-H, and twelve occur through cyclical transistion states, which eliminate products as hydrogen, ethene, acetaldehyde, ethane, ethyl alcohol, methyl ethyl ether, methane, some carbenes and also diradicals. These products had been considered to the determination of the activation barriers, enthalpies of reaction, entropies of reaction and free energy of Gibbs of reaction. Primary ways occurring through the break of bonds, had not reproduced experimental values for the activation barriers, however they had reproduced in a significant way, values of the enthalpy of the reaction. Elimination of ethene and ethyl alcohol, occurring by a transition state of four centers, presented the lowest activation barrier. Acetaldehyde and ethane elimination occurring through four centers, presented a high significantly barrier, but on the other hand it presented the smallest enthalpy, lightly exothermic above -0,8 kcal.mol-1. Eliminations 1,2 of methane and carbene occurring through three centers, together with the elimination 1,1 of hydrogen and carbene through three centers, elimination 2,2 of hydrogen and carbene through three centers and elimination 1,4 of hydrogen, acetaldehyde and ethene through six centers, had presented relatively next activation barriers, showing that they are competitive among themselves. The computed values of the channels that occur through cyclical transition states had been compared with the available experimental results and the trustworthiness of this computational boarding for the study of unimolecular reactions in multi-channel had been dicussed. Determination of thermochemical parameters, as heat of formation for radicalar species of the primary channel of decomposition and some alcoxyde radicais, together with the estimative of the electronic and protonic affinities,( with the ab initio Gaussian 2 boarding which estimate very precise eletronic energies ) and their results had been compared with the available experimental values and with values gotten through energies of bond and Benson\'s additivity rule.

Nous présentons des études expérimentales et théoriques de disiliciures alcalino-terreux, le disilane (Si2H6) et du carbone à haute pression. Nous étudions les disiliciures et en particulier le cas d’une phase plane de BaSI2 qui a une structure hexagonale avec des liaisons sp3 entre les atomes de silicium. Cet environnement électronique conduit à un gaufrage de feuilles du silicium. Nous démontrons alors une amélioration de la température de transition supraconductrice de 6 à 8.9 K lorsque les couches de silicium s’aplanissent dans cette structure. Des calculs ab initio basés sur DFT ont guidé la recherche expérimentale et permettent d’expliquer comment les propriétés électroniques et des phonons sont fortement affectés par les fluctuations du flambage des plans de silicium. Nous avons aussi étudié les phases cristallines de disilane à très haute pression et une nouvelle phase métallique est proposé en utilisant les méthodes de prédiction de structure cristalline. Les températures de transition calculées donnant un supraconducteur autour de 20 K à 100 GPa. Ces valeurs sont significativement plus faibles comparées à celles avancées dans la littérature. Finalement, nous présentons des études de structures de carbone à haute pression à travers une recherche de structure systématique. Nous avons trouvé une nouvelle forme allotropique du carbone avec une symétrie Cmmm que nous appelons Z-carbone. Cette phase est prévue pour être plus stable que le graphite pour des pressions supérieures à 10 GPa. Des expériences et simulation de rayon-X et spectre Raman sugèrent l’existence de Z-carbone dans des micro-domaines de graphite sous pression / We present experimental and theoretical studies of sp3 materials, alkaline-earth-metal (AEM) disilicides, disilane (Si2H6) and carbon at high pressure. First, we study the AEM disilicides and in particular the case of a layered phase of BaSi2 which has an hexagonal structure with sp3 bonding of the silicon atoms. This electronic environment leads to a natural corrugated Si-sheets. Extensive ab initio calculations based on DFT guided the experimental research and permit explain how electronic and phonon properties are strongly affected by changes in the buckling of the silicon plans. We demonstrate experimentally and theoretically an enhancement of superconducting transition temperatures from 6 to 8.9 K when silicon planes flatten out in this structure. Second, we investigated the crystal phases of disilane at the megabar range of pressure. A novel metallic phase of disilane is proposed by using crystal structure prediction methods. The calculated transition temperatures yielding a superconducting Tc of around 20 K at 100 GPa and decreasing to 13 K at 220 GPa. These values are significantly smaller than previously predicted Tc’s and put serious drawbacks in the possibility of high-Tc superconductivity based on silicon-hydrogen systems. Third, we studied the sp3-carbon structures at high pressure through a systematic structure search. We found a new allotrope of carbon with Cmmm symmetry which we refer to as Z-carbon. This phase is predicted to be more stable than graphite for pressures above 10 GPa and is formed by sp3-bonds. Experimental and simulated XRD, Raman spectra suggest the existence of Z-carbon in micro-domains of graphite under pressure

Thesis describes recent advances in the synthesis of donor-acceptor conjugated copolymers and their efficient doping via molecular p-dopants.

Thesis describes recent advances in the synthesis of donor-acceptor conjugated copolymers and their efficient doping via molecular p-dopants.:Chapter I Preface Motivation and Goals Outline 7 Chapter II 8 State of the Art & Characterization Techniques 8 2.1. General Introduction 8 2.1.1. Concept of Conjugated Polymers 9 2.1.2. Electronic Conduction and Necessity of Doping in Conjugated Polymers 11 2.1.3. Solubility and Processing. 14 2.2. Doping 17 2.2.1. Concept of Doping in Conjugated Polymers 17 2.2.2. Morphological Changes of the Material upon Doping. Conductivity. 20 2.2.3. State-of-the-art p-dopants. 23 2.3. Synthetic Strategies for the Design of (Semi)conducting Polymers 28 2.3.1. A Concise Review: from Polyacetylene till Modern DA Polymers 28 2.3.2. Synthetic Routes to Conjugated Polymers 31 2.3.3. Step-growth vs Chain-growth 34 2.3.4. Benchmark solution-processable Polymers 38 2.4. Characterization techniques 41 2.4.1. Conductivity Measurements 41 2.4.2. Electrochemical Voltammetry 42 2.4.3. Uv-vis-near-infrared 44 2.4.4. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. 44 2.4.5. Morphological studies. 45 2.4.6. Electron Spin Resonance Spectroscopy. 46 Chapter III 48 Results & Discussion 48 3.1. Diketopyrrolopyrrole-Based Copolymers 50 3.1.1. Motivation 50 3.1.2. Results and Discussion 51 3.1.4. Summary 89 3.2. Naphthalene Diimide-based Copolymer 90 3.2.1. Motivation 90 3.2.2. Results and Discussion 92 3.2.4. Summary 105 3.3. Isoindigo-Based Copolymers 107 3.3.1. Motivation 107 3.3.2. Results and Discussion 108 3.3.4. Summary 119 Summary & Conclusions 120 Outlook 123 Chapter IV 125 Experimental Part 125 4.1. General Methods and Instrumentation 125 4.2. Synthesis 129 4.2.1. Synthesis of diketopyrrolopyrrole copolymer. 129 4.2.2. Synthesis of electron-conducting polymer (PNDIT2) 132 4.2.3. Synthesis of polyisoIndigo 132 4.2.3. Synthesis of Dopants 135 4.3. Cyclic voltammetry measurements 136 4.4. GIWAX data. 143 4.5. Films preparation 145 References 147 Table of Abbreviations 159 List of Publications 161 Acknowledgements 162 Appendix 163

In der vorliegenden Diplomarbeit wurden sekundäre Isotopeneffekte auf NMR-chemische Verschiebungen mit ab-initio quantenchemischen Methoden bestimmt. Um die zu erwartenden Fehler verschiedener Methoden abschätzen zu können, wurden die sekundären Isotopeneffekte von Fluor(2-2H1)ethan auf HF, MP2 und CCSD(T)-Niveau mit tripel- und quadrupel-Zeta Basissätzen berechnet. Anhand der Ergebnisse dieser Rechnungen lässt sich zeigen, dass gauche und antiperiplanare Konformere bereits mithilfe von sekundären Isotopenverschiebungen unterschieden werden können, die auf HF/tz2p-Niveau berechnet wurden. Weiterhin wurde untersucht, ob es eine Abhängingkeit des Isotopeneffektes von den Diederwinkeln zwischen Deuterium- und Fluorsubstituenten gibt. Die sekundären Isotopeneffekte auf 19F-NMR-chemische Verschiebungen von exo- und endo-2-Fluornorbornanen mit Deuterium Substituenten in den endo-3, exo-3, syn-7 oder anti-7 Positionen wurden auf HF/tz2p-Niveau berechnet. Es wird gezeigt, dass die berechneten Isotopeneffekte an 2-Fluornorbornanen eine Identifizierung der verschiedenen Stereoisomere erlauben. / In the present Diploma thesis secondary isotope effects on NMR chemical shieldings were determined using ab-initio quantum chemical methods. In order to estimate errors of various methods, secondary isotope effects on fluoro(2-2H1)ethane were calculated at the HF, MP2 and CCSD(T) level of theory using triple- and quadruple zeta basis sets. On the basis of these calculations it can be shown that gauche and antiperiplanar conformers can already be distinguished by their secondary isotope shifts calculated at the HF/tz2p level of theory. Furthermore it was investigated, whether a dependency of the isotope effects on dihedral angles between the deuterium and the fluorine substituent exists. The secondary isotope effects on 19F chemical shifts of exo- and endo-2-fluoronorbornanes with deuterium subsituents in the endo-3, exo-3, syn-7 or anti-7 positions were calculated at the HF/tz2p level. It is shown that the calculated isotope effects of 2-fluoronorbornanes allow to identify various stereoisomers.

NaHCOO(aq) and NaDCOO(aq) solutions were measured using Raman spectroscopy from dilute to concentrated solutions at 23 °C in water and heavy water from 50 to 4300 cm−1. A concentrated NaHCOO solution in heavy water was also measured. The Raman band parameters of HCOO−(aq) and DCOO−(aq) such as peak position, full width at half maximum (fwhm), integrated intensities, and depolarization values were determined. From the Raman spectroscopic data, it was concluded that the HCOO−(aq) and DCOO−(aq) symmetry is lower than C2v and probably as low as C1. In contrast to the solution state, (HCO2−(DCO2−) possess C2v symmetry in the gas phase and the DFT frequencies are given. DFT frequencies on a cluster of HCOO−/DCOO− with five implicit water molecules in the first sphere and placed in a polarizable continuum deviate not more than 1–2% from the measured ones. In the Raman spectrum in NaHCOO(aq), a band doublet at 2730 cm−1 and 2820 cm−1 occurs instead of a single band. The band doublet is due to Fermi resonance and results from the interaction of the overtone of the bending C–H mode, 2ν6 at 1382 cm−1 and ν1. The undisturbed C–H stretching mode, ν1 amounts to 2785 cm−1. In DCOO−(aq), a Fermi doublet was also observed at 2030.5 and 2116.5 cm−1, and the undisturbed wavenumber position amounts to 2101 cm−1. Furthermore, a solution of HCOO− in D2O showed slightly changed frequencies compared with the ones in water caused by the solvent isotope effect. Ion pairing between Na+ and HCOO− characterizes the Raman spectrum at high solute concentrations which are melt-like enabling direct contact between the ions. A NaHCOO solution with high amounts of LiCl added showed large perturbations of the HCOO− bands especially νsCOO− and δ COO− of HCOO−and revealed a stronger affinity of Li+ toward HCOO−. The ion pairs formed are most likely contact ion pairs between Li+ and HCOO− which have different stoichiometry of Li+: HCOO− such as 1:1 and 2:1.

This thesis investigates sustainability measures for quicklime and cement clinker production. It is the aim of this thesis to contribute to the effort of creating a more sustainable modus of industrial production. The methods used comprises process simulations through multicomponent chemical equilibrium calculations, fuel characterization and raw materials characterization through dynamic rate thermogravimetry. The investigated measures relate to alternative fuels, co-combustion, oxygen enrichment, oxyfuel combustion, mineral carbonation and optimizing raw material mixes based on thermal decomposition characteristics. The predictive multicomponent chemical equilibrium simulation tool developed has been used to investigate new process designs and combustion concepts. The results show that fuel selection and oxygen enrichment influence energy efficiency, and that oxyfuel combustion and mineral carbonation could allow for considerable emission reductions at low energy penalty, as compared to conventional post-combustion carbon dioxide capture technologies. Dynamic rate thermogravimetry, applied to kiln feed limestone, allows for improved feed analysis with a deeper understanding of how mixing of different feed materials will affect the production processes. The predictive simulation tool has proven to be of practical value when planning and executing production and full scale campaigns, reducing costs related to trial and error. The main conclusion of this work is that several measures are available to increase the sustainability of the industry.

The aim of this work was to assess the suitability of vibrational spectroscopic techniques (Raman, FT-IR and FT-NIR spectroscopy) as a means for the solid-state structural analysis of pharmaceuticals. Budesonide, fluticasone propionate, salbutamol hemisulfate, terbutaline hemisulfate, ipratropium bromide, polymorphic forms of salmeterol xinafoate and two polymorphic forms of sulfathiazole were selected since they are used in the management of certain respiratory disorders and from different chemical and pharmacological entities along with some pharmaceutical excipients. Conventional visual examination is not sufficient to identify and differentiate spectra between different pharmaceuticals. To confirm the assignment of key molecular vibrational band signatures, quantum chemical calculations of the vibrational spectra were employed for better understanding of the first five selected drugs. The nondestructive nature of the vibrational spectroscopic techniques and the success of quantum chemical calculations demonstrated in this work have indeed offered a new dimension for the rapid identification and characterisation of pharmaceuticals and essentially warrant further research. The application of simultaneous in situ Raman spectroscopy and differential scanning calorimetry for the preliminary investigation of the polymorphic transformation of salmeterol xinafoate polymorphs and two polymorphic forms of sulfathiazole has also been explored in this work leading to the development of a new method for the solid-state estimation of the transition temperature of entantiotropically related pharmaceutical polymorphs which represents the first analytical record of the use of this approach for pharmaceutical polymorphs.