Complexes of 2,2-cis [Rh2(N{C6H5}COCH3)4] bound to benzonitrile, ortho-tolunitrile, and meta-tolunitrile were synthesized and characterized using X-ray crystallography, IR spectroscopy, and proton NMR. The crystal structures of 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NCC6H5, 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{2-CH3}C6H4, and 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{3-CH3}C6H4 were solved using a Rigaku Mercury375R/M CCD XtaLab Mini Diffractometer. The 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NCC6H5 complex had unit cell dimensions of a=10.2115(7) Å, b=9.9667(7) Å, c=21.367(2) Å, and β=100.971(7)° with a P21/n space group. The 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{2-CH3}C6H4 complex had unit cell dimensions of a=10.3625(8) Å, b=10.0489(7) Å, c=21.611(2) Å, and β=100.868(7)° with a P21/n space group. The 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{3-CH3}C6H4 complex had unit cell dimensions of a=10.849(3) Å, b=11.530(3) Å, c=12.259(3) Å, α=117.562(8)°, β=103.061(7)°, and γ=101.562(7)° with a P-1 space group. Each rhodium atom had approximate octahedral coordination and was bound to another rhodium atom along with two equatorially bound nitrogens and two equatorially bound oxygens and one axially bound nitrogen that was a part of the nitrile.

Placing degree constraints on the vertices of a path allows the definitions of uphill and downhill paths. Specifically, we say that a path π = v1, v2,...vk+1 is a downhill path if for every i, 1 ≤ i ≤ k, deg(vi) ≥ deg(vi+1). Conversely, a path π = u1, u2,...uk+1 is an uphill path if for every i, 1 ≤ i ≤ k, deg(ui) ≤ deg(ui+1). We investigate graphical parameters related to downhill and uphill paths in graphs. For example, a downhill path set is a set P of vertex disjoint downhill paths such that every vertex v ∈ V belongs to at least one path in P, and the downhill path number is the minimum cardinality of a downhill path set of G. For another example, the downhill domination number of a graph G is defined to be the minimum cardinality of a set S of vertices such that every vertex in V lies on a downhill path from some vertex in S. The uphill domination number is defined as expected. We determine relationships among these invariants and other graphical parameters related to downhill and uphill paths. We also give a polynomial time algorithm to find a minimum downhill dominating set and a minimum uphill dominating set for any graph.

Mira-type stars are luminous red giants that have pulsation periods that last anywhere between 100 and 700 days. The irregular behavior of their periods and atmospheric properties flag them as excellent candidates for astrophysical studies of non-spherical stars. This paper focuses on the linear polarization of light emitted from three Mira- type stars: Mira itself, R Leo, and V CVn. Polarimetric data from the University of Wisconsin’s Half-Wave Spectropolarimeter (HPOL) database, as well as other archives of polarimetric data, provide us with insight into the atmospheric and geometrical prop- erties of these three stars. We were able to study the net polarizations and position angles alongside light curves provided by AAVSO. The observed variable polarization is a clear signature of evolving aspherical geometries for these stars. However, we found a major surprise concerning the polarimetric characteristics in V CVn, which suggest that V CVn is unlike a traditional Mira-type variable star. We end with an exploration of new possibilities regarding the atmospheric properties of V CVn.

No abstract.

The objective of my thesis was to add to a catalogue of molecular structures that is being compiled as a part of the Standoff Detection Project. The optimized geometry of P8O20 and P20O20 were calculated using restricted Hartree-Fock Theory, using the standard quantum mechanics and computational chemistry programs ECCÈ and NWChem. Unfortunately, due to the extremely time consuming nature of these calculations there was not enough time to complete the calculations for P24O48 and P24O60.

Photodynamic therapy (PDT) employs photosensitizing drugs for treating cancer. Once introduced into the body and localized in tumor cells, these photosensitizers are irradiated with light to produce active singlet oxygen radicals which kill cancer cells. The current drugs used in PDT have low quantum yield and always require a high energy radiation (normally laser). There is always a need for more effective drugs that have a high quantum yield and can be activated by visible light, in order to eliminate side effects caused by laser radiations. In this work we synthesized derivatives of phenothiazine and phenothiazinium chromophores from the commercially available phenothiazine (1). These derivatives include: 3,7-dibromophenothiazinium perbromide (2), N-acetyl phenothiazine (5), N-acetyl-3,7-dibromophenothiazine (6), 3,7-dinitrophenothiazine (10), N-acetyl-3,7-dinitrophenothiazine (11), N-acetyl-3,7-diaminophenothiazine (12), thionine chloride (15) and 3,7-phenothiaziniumdinitrile (14). Synthesis of 3,7-phenothiazinium dicarboxylic acid was attempted using 1 and 15 as starting materials by exploring various synthetic routes for carboxylic acids.

GaN belongs to the group III nitrides and is today the material of choice for efficient blue light emission, enabling solid state white lighting by combining red, blue and green light emitting diodes (LED) or by having a blue LED illuminating a phosphor. By combining GaN quantum well (QW) structures with colloids, nanoparticles or polyfluorene films, LEDs may be fabricate at lower cost. Such hybrid structures are promising for future micro-light sources in full-color displays, sensors and imaging systems. In this work, hybrid structures based on an MOCVD grown GaN QW sandwiched between two layers of AlGaN have been studied. On top of the structure, colloidal ZnO nano-crystals were deposited by spin-coating. Time-resolved photoluminescence was used to investigate the QW exciton dynamics in these hybrids depending on the cap layer thickness. From comparison of the recombination rate in the bare QW structure and the hybrid, the efficiency of the non-radiative resonant energy transfer between the QW and the nano-crystals could be obtained. Bulk GaN of large area is difficult to synthesize. Thus, due to lack of native substrates, GaN-based structures are grown on SiC or sapphire, which results in high threading dislocation density in the active layer of the device. Fabricating GaN nanorods (NR) can be a way to produce GaN with lower defect density since threading dislocations are annihilated toward the NR wall during growth. Here, GaN(0001) NRs grown on Si(111) substrates by magnetron sputter epitaxy using a liquid Ga target have been investigated. Sputter deposition has the advantage of being easy to scale up for depositions on large surfaces. It is also possible to deposit at lower temperatures, which allows the use of substrates with lower decomposition temperature. In the second paper of this thesis, optical and structural properties of sputtered GaN NRs have been studied.

The scope of this licentiate thesis is the investigation of carbon based thin films suitable for rolling components, especially roller bearings. Carbon and carbon nitride are materials with advantageous tribological properties and high resiliency. Such materials are required in order to withstand the demanding conditions of bearing operation, such as high loads and corrosive environments. A fundamental condition for coated bearings is that the deposition temperature must be striktly limited. Thus, carbon nitride (CNx) thin films were synthesized here at low temperature of 150 oC by different reactive magnetron sputtering techniques, which are mid-frequency magnetron sputtering (MFMS), direct current magnetron sputtering (DCMS), and high power impulse magnetron sputtering (HiPIMS). While DCMS is a very well studied technique for carbon based films, MFMS and HiPIMS are relatively new sputtering techniques for carbon, and especially CNx depositions. Using different magnetron sputtering techniques, different ionization conditions prevail in the chamber during each process and influence the obtained film properties at a great extent. It was found that bias duty cycles and the amount of working gas ions are key parameters and affect the morphology and microstructure as well as the mechanical response of the films. Moreover, different bias voltages, from 20 V up to 120 V were applied during the processes in order to investigate the changes that the different ion energies induce in the film structure. The structural, mechanical and tribological properties of CNx films are also presented in this licentiate thesis. The morphology of CNx films strongly depends on both the deposition technique and ion energy. The special configuration of MFMS mode produces highly homogeneous and dense films even from low applied bias voltages, while in HiPIMS mode high bias voltages above 100 V must be applied in order to produce films with similar structural characteristics. DCMS is also proven as a good technique for homogeneous and dense films. Low bias voltages do not favor  homogeneous structures, thus at 20 V all techniques produced films with columnar structures with intercolumnar voids. High bias voltages influence the N incorporation in the films, with the appearance of re-sputtering of N-containing species and a promotion of sp2 bonding configurations with increasing ion energy. Nevertheless, the different deposition mode influences the sp2 content in different ways, with only MFMS showing a clear increase of sp2 content with increasing bias voltage and HiPIMS showing relatively constant sp2 content. The morphology and microstructure of the CNx films affects their mechanical response, with higher ion energies producing harder films. A dependency of hardness and elastic modulus with increasing ion energy was obtained, where for all deposition modes, hardness and elastic modulus increase linearly with increasing bias voltage. Films with hardness as high as 25 GPa were synthesized by MFMS at 120 V , while the softer film yielded a hardness of 7 GPa and was deposited by HiPIMS at 20 V . The elastic recovery of the films differs with increasing ion energies, presenting a correlation with the C sp2 bond content. The highest elastic recovery of 90% was extracted for the film deposited by MFMS at 120 V and is a value similar to the elastic recovery obtained for FL-CNx films. All films developed compressive residual stresses, depending also on the ion energies and the deposition mode used. It is demonstrated that the induced stresses in the films increase when denser and more homogeneous film morphologies are obtained and with higher Ar intercalcation. Low friction coefficients were obtained for all films between 0.05 and 0.07, although the deposition conditions are not detrimental for the development of friction coefficient. The wear resistance of the films was found to be dependent on the morphology and to some extent on the microstructure of the films. Harder, denser, and more homogeneous films have higher wear resistance. Especially, CNx films deposited by MFMS at 120 V present no wear. The tribological characteristics of the surface of the films were also investigated at nanoscale by a new reciprocal wear test. In this wear test, the recording of the track profile is performed in between consecutive test cycles, eliminating also thermal drift. The very low wear of the films deposited by MFMS at 100 V and 120 V revealed that during the wear test a phase transformation on the surface may take place, possibly graphitization. It is also demonstrated the way that the surface characteristics, such as asperities and roughness affects the tribological measurements. Attention is also turned to the presence of large asperities on the film surface and the way they affect the obtained average friction coefficient and tribological measured data. / <p>The series name <em>Linköping Studies in Science and Technology Licentiate Thesis</em> is incorrect. Correct series name is <em>Linköping Studies in Science and Technology. Thesis</em>.</p>

This thesis is a theoretical study of configurationally disordered icosahedral boronrich solids, in particular boron carbides, using density functional theory and alloy theory. The goal is to resolve discrepancies, regarding the properties of boron carbides, between experiments and previous theoretical calculations which have been a controversial issue in the field of icosahedral boron-rich solids. For instance, B13C2 is observed experimentally to be a semiconductor, meanwhile electronic band structure calculations reveal a metallic character of B13C2 due to its electron deficiency. In B4C, on the other hand, the experimentally observed band gap is unexpectedly smaller, not the usual larger, than that of standard DFT calculations. Another example is given by the existence of a small structural distortion in B4C, as predicted in theoretical calculations, which reduces the crystal symmetry from the experimentally observed rhombohedral (R3m) to the based-centered monoclinic (Cm). Since boron carbide is stable as a single-phase over a broad composition range (~8-20 at.% C), substitution of boron and carbon atoms for one another is conceivable. For this reason, the discrepancies have been speculated in the literature, without a proof, to originate from configurational disorder induced by substitutional defects. However, owing to its complex  atomic structure, represented by 12-atom icosahedra and 3-atom intericosahedral chains, a practical alloy theory method for direct calculations of the properties of the relevant configurations of disordered boron carbides, as well as for a thermodynamic  assessment of their stability has been missing. In this thesis, a new approach, the superatom-special quasirandom structure (SA-SQS), has been developed. The approach allows one to model configurational disorder in boron carbide, induced by high concentrations of low-energy B/C substitutional defects. B13C2 and B4C are the two stoichiometries, mainly considered in this study, as they are of particular importance and have been in focus in the literature. The results demonstrate that, from thermodynamic considerations, both B13C2 and B4C configurationally disorder at high temperature. In the case of B13C2, the configurational disorder splits off some valence states into the band gap that in turn compensates the electron deficiency in  ordered B13C2, thus resulting in a semiconducting character. As for B4C, the configurational disorder eliminates the monoclinic distortion, thus resulting in the restoration of the higher rhombohedral symmetry. Configurational disorder can also account for an excel lent agreement on elastic moduli of boron carbide between theory and experiment. Thus, several of the previous discrepancies between theory and experiments are resolved. Inspired by attempts to enhance the mechanical properties of boron suboxide by fabricating boron suboxide-boron carbide composites, as recently suggested in the literature, the SA-SQS approach is used for modeling mixtures of boron suboxide (B6O) and boron carbide (B13C2), denoted by pseudo-binary (B6O)1–x(B13C2)x alloys. The knowledge of configurational disorder, gained from the previous studies of boron carbide, is applied to model the mixing alloys. By investigating the thermodynamics of mixing between B6O and B13C2, the phase diagram of the (B6O)1–x(B13C2)x alloys is outlined and it reveals the existence of a miscibility gap at all temperatures up to the melting point, indicating the coexistence of B6O-rich and either ordered or disordered B13C2-rich domains in (B6O)1–x(B13C2)x alloys under equilibrium condition. However, a limited intermixing of B6O and B13C2 to form solid solutions at high temperature is predicted, e.g. a solid solution of ~5% B13C2 in B6O and ~20% B6O in B13C2 at 2000 K.

This thesis concerns the wear resistant coating TiSiN and the development of the analysis technique atom probe tomography (APT) applied to this materials system. The technique delivers compositional information through time-of-flight mass spectrometry, with sub-nanometer precision in 3D for a small volume of the sample. It is thus a powerful technique for imaging the local distribution of elements in micro and nanostructures. To gain the full benefits of the technique for the materials system in question, I have developed a method that combines APT with isotopic substitution, here demonstrated by substitution of natN with 15N. This alters the time-of-flight of ions with of one or more N and will thereby enable the differentiation of the otherwise inseparable isotopes 14N and 28Si. Signs of small-scale fluctuations in the data led the development of an algorithm needed to properly visualize these fluctuations. A method to identify the best sampling parameter for visualization of small-scale compositional fluctuations was added to an algorithm originally designed to find the best sampling parameters for measuring and visualizing strong compositional variations. With the identified sampling parameters, the nano-scale compositional fluctuations of Si in the metal/metalloid sub-lattice could be visualized. The existence and size of these fluctuations were corroborated by radial distribution functions, a technique independent of the previously determined sampling parameter. The radial distribution function algorithm was also developed further to ease in the interpretation. The number of curves could thereby be reduced by showing elements, rather than single and molecular ions (of which there were several different kinds). The improvement of the algorithm also allowed interpretation of signs regarding the stoichiometry of SiNy. With a combination of analytical transmission electron microscopy and APT we show Si segregation on the nanometer scale in arc-deposited Ti0.92Si0.0815N and Ti0.81Si0.1915N thin films. APT composition maps and proximity histograms generated from Ti-rich domains show that the TiN contain at least ~2 at. % Si for Ti0.92Si0.08N and ~5 at. % Si for Ti0.81Si0.19N, thus confirming the formation of solid solutions. The formation of relatively pure SiNy domains in the Ti0.81Si0.19N films is tied to pockets between microstructured, columnar features in the film. Finer SiNy enrichments seen in APT possibly correspond to tissue layers around TiN crystallites, thus effectively hindering growth of TiN crystallites, causing TiN renucleation and thus explaining the featherlike nanostructure within the columns of these films.