No description available.

Nuclear magnetic resonance (NMR) is a popular spectroscopic method and has widespread use in many fields. Recent developments in solid-state NMR have increased interest in experiment and, alongside simultaneous developments in computational theory, have led to the field dubbed 'NMR crystallography.' This is a suite of methodologies, complementing the capabilities of other crystallographic methods in the determination of atomic structure, especially when large crystals cannot be made and when exploring materials with phenomena such as compositional, positional and dynamic disorder. NMR J-coupling is the indirect coupling between nuclear spins, which, when measured, can reveal a wealth of information about structure and bonding. This thesis develops and applies the method of Joyce for the prediction of NMR J-coupling in condensed matter systems using plane-wave pseudopotential density-functional theory, an important requirement for efficient treatment of finite and infinite periodic systems. It describes the first-ever method for the use of ultrasoft pseudopotentials and inclusion of special relativistic effects in J-coupling prediction, allowing for the treatment of a wider range of materials systems and overall greater user friendliness, thus making the method more accessible and attractive to the wider scientific community.

Computational approaches play an important role in today's materials science owing to the remarkable advances in modern supercomputing architecture and algorithms. Ab initio simulations solely based on a quantum description of matter are now very able to tackle materials problems in which the system contains up to a few thousands atoms. This dissertation aims to address the modern electronic structure calculation methods applied to a range of various materials such as liquid and amorphous phase materials, nanostructures, and small organic molecules. Our simulations were performed within the density functional theory framework, emphasizing the use of real-space ab initio pseudopotentials. On the first part of our study, we performed liquid and amorphous phase simulations by employing a molecular dynamics technique accelerated by a Chebyshev-subspace filtering algorithm. We applied this technique to find l- and a- SiO₂ structural properties that were in a good agreement with experiments. On the second part, we studied nanostructured semiconducting oxide materials, i.e., SnO₂ and TiO₂, focusing on the electronic structures and optical properties. Lastly, we developed an efficient simulation method for non-contact atomic force microscopy. This fast and simple method was found to be a very powerful tool for predicting AFM images for many surface and molecular systems. / text

Die elektrischen Mikrofeldverteilungen (EMDs) und ihre Auswüchse wurden in einkomponentiger (OCP) Elektron-, zweikomponentigen (TCP) Elektron-Positron-, Wasserstoff- und einwertig ionisierten Alkaliplasmen im Rahmen verschiedener Pseudopotentialmodelle (PM) untersucht und mit sowohl Molekulardynamik (MD) und Monte-Carlo Simulationen als auch mit Experimenten vergliechen. Die verwendeten theoretischen Verfahren zur Berechnung von EMDs gehen zurück auf die von C. A. Iglesias entwickelte Kopplungsparameter Integrationstechnik (KPIT) für OCP und die von J. Ortner et al. vorgeschlagene verallgemeinerte KPIT für TCP. EMDs wurden im Rahmen der abgeschirmten Kelbg-, Deutsch-, Hellmann-Gurskii-Krasko(HGK)-PM untersucht, welche quantenmechanische Effekte, Abschirmungseffekte und die Struktur der Ionenrümpfe (HGK) berücksichtigen. Die Abschirmungseffekte wurden auf Grundlage der Bogoljubov-Born-Green-Kirkwood-Yvon- Methode eingeführt. Wir haben das abgeschirmte HGK-Pseudopotential in der Debye-Näherung sowie in einer mäßig gekoppelten Plasma-Näherung verwendet. Wir haben verschiedene Typen vom asymptotischen Verhalten der Verteilungsauswüchse in Abhangigheit von Plasmaparameter, Plasmatypen und Strahler bestimmt. Der Vergleich der experimentell gewonnenen Daten mit sowohl einem synthetischen Li2+-Lyman-Spektrum als auch mit einer synthetischen Li II 548 nm Linie lassen den Schluss zu, daß die EMD, welche auf der Grundlage der Iglesias-Methode für OCP im HGK-PM und der MD erhalten wurde, eine gute Übereinstimmung mit den experimentellen Werten liefert. Die statischen partiellen und Ladung-Ladung-Strukturfaktoren (SSF) wurden für Alkali- und Be2+-Plasmen unter Verwendung der von G. Gregori et al. beschriebenen Methode berechnet. Die dynamischen Strukturfaktoren (DSF) für Alkaliplasmen wurden unter Verwendung der durch V. M. Adamyan et al. entwickelten Methode der Momente berechnet. Bei beiden Methoden wurde das abgeschirmte HGK-Pseudopotential verwendet. / The electric microfield distributions (EMDs) and its tails have been studied for electron one-component plasma (OCP), electron-positron, hydrogen and single-ionized alkali two-component plasmas (TCP) in a frame of different pseudopotential models (PM) and compared with Molecular Dynamics (MD) and Monte-Carlo simulations as well as with experiments. The theoretical methods used for calculation of EMDs are a coupling-parameter integration technique (CPIT) developed by C. A. Iglesias for OCP and the generalized CPIT proposed by J. Ortner et al. for TCP. We studied the EMDs in a frame of the screened Kelbg, Deutsch, Hellmann-Gurskii-Krasko (HGK) PMs which take into account quantum-mechanical, screening effects and the ion shell structure (HGK) due to the Pauli exclusion principle. The screening effects were introduced on a base of Bogoljubov-Born-Green-Kirkwood-Yvon method. We used the screened HGK pseudopotential in the Debye approximation as well as in a moderately coupled plasma approximation. The influence of the plasma coupling parameter on the EMD along with the ion shell structure was investigated. We determined different types of asymptotic behaviour of EMD tails in dependence on the plasma type, parameters and radiator. Comparison of a synthetic Li2+ Lyman spectrum as well as comparison of a synthetic Li II 548 nm line with experimental data allows us to conclude that the EMD, obtained on a base of the CPIT method for OCP within the HGK PM and MD, provides a good agreement with the experiment. We have calculated the partial and charge-charge static structure factors (SSF) for alkali and Be2+ plasmas using the method described by G. Gregori et al.. We have calculated the dynamic structure factors (DSF) for alkali plasmas using the method of moments developed by V. M. Adamyan et al. In both methods the screened HGK pseudopotential has been used.

The electronic properties of Triphenylamine (TPA) in gas phase and adsorbed on gold(111) have been simulated with Quantum Espresso using Density Functional Theory (DFT). To better understand how the presence of a gold surface affects sunlight absorption in the system, partial Density Of States (pDOS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) of the system have been calculated. To describe the electronic excitation, three different methods have been used, No Core Hole (NCH), Full Core Hole (FCH) and Half Core Hole (HCH) approximation. The excitation of the TPA molecule was made in the nitrogen (N) atom and in the four different carbon (C) atoms with different electronic environments, C-ipso, C-ortho, C-meta and C-para. When using the HCH method, the absorbing atom must be described by a pseudopotential (PP) which includes half of a hole in the 1s orbital. This PP has been generated and a detailed summary of the process is described. The TPA/gold system relaxes to a position with the central N atom of TPA above an gold (Au) atom in the second layer of the surface and at a distance of 3.66 Angstrom, to the first layer. TPA keeps its symmetry with only small differences in the length of atomic bonds when adsorbed. The most striking result of this study is how the band gap of TPA is affected by the gold layer. From the pDOS we can observe that TPA in gas phase has a clear band gap of 2.2 eV with C-ortho dominating in the valence region and the four carbons dominating in the first unoccupied states. When depositing the molecule on the surface of Au(111), the band gap is essentially gone and a number of states appear between the previous highest occupied and lowest unoccupied molecular orbital in TPA. These new states align in energy with three clusters of states of the gold suggesting an interaction between the molecule and the surface. In the generated NEXAFS of nitrogen and carbon in TPA gas phase, one can observe a small pre-peak before the first unoccupied state. This is reinforced when adsorbing the molecule, which generates a pre-peak of approximately 3 eV in width. The pre-peak is connected to the new peaks seen in pDOS, correlating with experimental results on the same system.