Introdução: As doenças que envolvem a órbita representam um complexo problema cirúrgico, principalmente as localizadas no ápice orbitário, por onde passam estruturas críticas e um espaço pequeno. O uso do endoscópio por via endonasal para abordagem cirúrgica das lesões do ápice orbitário é uma técnica recente, com poucas citações na literatura. É necessário o estudo de referências anatômicas objetivas que tornem a cirurgia mais segura. Objetivo: Descrever os parâmetros anatômicos utilizados na abordagem cirúrgica endonasal endoscópica, assim como avaliar a concordância entre os hemicrânios do mesmo cadáver e as diferenças conforme o gênero. Casuística e métodos: Estudo anatômico em 30 cadáveres adultos, ambas as fossas nasais foram dissecadas (n=60 hemicrânios). Sob visibilização endoscópica endonasal, realizou-se a dissecção do ápice orbitário. Mensuramos a distância entre a crista etmoidal e o arco coanal para o forame óptico e para a fissura orbitária superior. Os resultados foram registrados na ficha de protocolo do estudo. Resultados: Foram dissecados 30 cadáveres, 60 hemicrânios ou lados. O sexo masculino foi mais prevalente, representando 63,3% dos cadáveres (19/30), enquanto o sexo feminino representou 36,7% (11/30). 43,3% dos cadáveres eram da raça branca (13/30), 20%, pardos (6/30), e 36,7%, negros (11/30). A correlação entre os valores conforme o lado nas seguintes aferições foi observada: Crista etmoidal - Forame óptico, (r=0,748, p=0.0001); Crista etmoidal - Fissura Orbitária Superior (r=0.785, p=0.0001), Arco coanal - Forame óptico (r=0,835, p=0.0001); Arco coanal - Fissura orbitária superior (r=0.820, p=0.0001). Foi obtido um Kappa de 0,444 na avaliação da concordância entre os lados em relação ao posicionamento da artéria etmoidal anterior no forame óptico. Conclusões: A sistematização da abordagem do ápice orbitário facilita seu acesso cirúrgico e a compreensão da anatomia. A crista etmoidal e o arco coanal se mostraram estruturas relevantes e com medidas constantes nos cadáveres estudados. Os valores do coeficiente de correlação de Spearman (r) foram maiores que 0,7, o que revela uma boa correlação entre as medidas dos hemicrânios do mesmo indivíduo. Ao analisarmos a concordância do posicionamento da artéria oftálmica entre os hemicrânios de um mesmo cadáver, podemos observar que a concordância foi moderada, o que representa assimetria e variação de localização da artéria. Ao compararmos as medidas aferidas entre os lados, observou-se que os valores são semelhantes e não houve diferença estatística das distâncias em nenhuma das referências anatômicas propostas para o estudo / Introduction: Diseases that affect the orbit pose a complex surgical challenge, particularly those involving the orbital apex, a small space through which critically important structures course. Endoscopic endonasal approaches to the surgical treatment of orbital apex lesions are a recent technique, with few citations in the literature. Research is still needed into objective anatomic landmarks that can improve surgical safety. Objective: To describe the anatomic landmarks used in endoscopic endonasal surgical approaches and assess agreement between placement of these landmarks in midsagittal sections of cadaver skulls and potential gender differences. Materials and methods: In this anatomic study, the nasal fossae of 30 adult cadavers were dissected (n=60 half-skulls). The orbital apex was dissected under endoscopic endonasal visualization. The distances between the ethmoidal crest and choanal arch to the optic foramen and to the superior orbital fissure were measured and recorded. Results: Overall, 30 cadavers were dissected for a total of 60 half-skulls or sides. The sample was predominantly male (63.3%, 19/30 cadavers); females accounted for the remaining 36.7% (11/30). Regarding skin color, 43.3% of cadavers were white (13/30), 20% were brown (6/30), and 36.7% were black (11/30). The following correlations between measurements according to side were observed: ethmoidal crest to optic foramen, r=0.748 (p=0.0001); ethmoidal crest to superior orbital fissure, r=0.785 (p=0.0001); choanal arch to optic foramen, r=0.835 (p=0.0001); choanal arch to superior orbital fissure, r=0.820 (p=0.0001). Analysis of the agreement of ophthalmic artery location within the optic foramen between skull halves revealed a kappa of 0.444. Conclusions: The approach systematization to the orbital apex will facilitate surgical access and improve understanding of the anatomy. In the cadavers studied in this sample, the ethmoidal crest and choanal arch were relevant structures and exhibited consistent measurements. Spearman correlation coefficients (r) were greater than 0.7, which is indicative of good correlation between measurements obtained in the skull halves of each cadaver. Analysis of the position of the ophthalmic artery in each skull half of the same cadaver revealed moderate agreement, which indicates asymmetry and variation in the location of this artery. Comparison of the measurements obtained in different sides showed similar values, with no statistically significant differences in the distances between any of the proposed anatomic landmarks

Einen Orbitadefekt mit Verlust des Auges und der filigranen Lidstrukturen kann eine implantatverankerte Silikonepithese im Halt sicher und bei geöffnetem Auge ästhetisch mit gutem Ergebnis abdecken. Bei Lidschluß fällt allerdings die Starrheit der Lider in der Epithese auf. Ziel der Entwicklung war es, das künstliche Oberlid in der Orbitaepithese beweglich zu gestalten und so durch die gewonnene Dynamik ein natürlicheres Aussehen beim Patienten zu erreichen. In der Epithese sollten alle Komponenten integriert sein, um das künstliche Oberlid synchron zum gesunden Auge zu bewegen. Als bewegliches Oberlid erwies sich gegossene Latexmilch als Material am geeignetsten. Dieses Material war elastisch, einfärbbar und konnte den Belastungen der ungefähr 30 unwillkürlichen Lidschlagbewegungen pro Minute standhalten. Das künstliche Oberlid wurde analog dem natürlichen Vorbild des Lidöffners nach dem Prinzip der Zuggurtung über die Augenprothese nach oben hinten gezogen. Als Antrieb wurde ein DC-Mikromotor eingesetzt, der das Oberlid mit Hilfe eines kleinen Polyamidfadens, welcher an der inneren verstärkten Lidkante befestigt war, nach kranial bewegte. Der Faden wurde über eine Kanülenführung auf eine Seilrolle gewickelt. Nachdem sich ein aufgebautes Tischmodell im Test bewährt hatte, wurde eine einbaufähige elektronische Schaltung in SMD-(Surface Mounted Device) Technik entwickelt, die einerseits den Antrieb steuerte und andererseits die zur Synchronisation erforderlichen Muskelpotentiale verarbeitete. Diese zwei doppelseitig bestückten Platinen wurden direkt hinter die individuell aus Glas vom Okularisten hergestellte Augenprothese positioniert. Über fünf integrierte einstellbare Potentiometer konnten die abgeleiteten Muskelsignale für eine verzögerungsfreie Lidbewegnung beim Patienten individuell verändert werden. Die Energiebereitstellung für die Elektronik und den Motor konnte aufgrund der zu niedrigen Nennkapazitäten nicht durch Akkumulatoren erfolgen, sondern wurde durch eine kleine leicht auswechselbare Batterie erreicht, die hochgerechnet Strom für 7 bis 14 Tage lieferte. Da die einzelnen Komponenten nicht frei in der Epithese liegen konnten, wurde als Schutz ein Gehäuse in hartem Acrylatkunststoff konzipiert. Da die Anordnung der Batterie unter oder hinter dem Motor möglich war und auch die Elektronik versetzt zu Batterie und Motor angebracht werden konnte, konnte so die Geometrie des Gehäuses in Grenzen dem individuellen Orbitadefekt angepaßt werden. In klinischen Versuchen an gesunden Probanden und Patienten mit implantatverankerten Orbitaepithesen zeigte sich, daß Muskelpotentiale vom M. orbicularis oculi aus dem gesunden Oberlid oder teilweise der exenterierten Orbita mit Restaktivität des Lidschließers mit Nadelelektroden bipolar abgeleitet zur Ansteuerung des Motors geeignet waren. Mit diesen Biopotentialen wurde das reibungslose Funktionieren der synchronen Lidbewegung des Prototypen an einer freiwilligen gesunden Versuchsperson getestet. Nach umfangreichen Labortestungen wurden zwei Patienten mit dieser neuartigen Orbitaepithese rehabilitiert. Bei den Patienten wurde das passende Gehäuse mit den gekapselten Funktionseinheiten individuell hergestellt und dieses in eine Silikonepithese eingearbeitet. Gehalten wurde die Silikonepithese über implantatfixierte Magnetabutments. Die Muskelpotentialableitung zur Triggerung der synchronen Lidbewegung erfolgte durch eine intramuskuläre EMG - Ableitung des M. orbicularis oculi. Beim ersten Patienten gelang dieses über eine sterile Nadelelektrode, die allerdings beim Tragen der neuen Orbitaepithese jedes Mal neu in den Muskel eingestochen werden mußte. Beim zweiten Patienten wurden die Muskelpotentiale über eine subcutan implantierte dünne EMG - Elektrode aufgenommen. Die Myosignale wurden bei beiden Patienten bipolar abgeleitet. Die zweite differente Elektrode kontaktierte einen implantatfixierten Magneten. Die Neutralelektrode war mit einem weiteren implantatverankerten Magneten verbunden. Die abgeleiteten Muskelimpulse beim Lidschlag konnten so bei den Patienten eine zum gesunden Oberlid synchrone künstliche Lidbewegung initiieren. Da die Bauteile zur künstlichen Lidbewegung noch nicht beliebig klein zu gestalten sind, können zur Zeit noch nicht alle Orbitaepithesenträger mit der neuartigen Epithese rehabilitiert werden. Um bei Patienten mit kleineren Orbitadefekten die Epithese eingliedern zu können, muß sich die zukünftige Forschung auf eine noch weitere Größenreduktion der einzelnen Komponenten konzentrieren. Durch die Entwicklung von telemetrischen Verfahren wird es möglich sein, die von einer intramuskuären implantierten, für diese Anwendung optimierten EMG - Elektrode emfangenen Signale ohne infektionsgefährdete Hautdurchleitung zur Epithese zu übertragen. / An orbit defect with loss of the eye and its delicate lid structures can be concealed with an implant anchored silicon facial prosthesis. This method assures secure retention and good esthetic results as long as the eye remains open. However, when the healthy lid closes, the immobility of the prosthesis becomes conspicuous. The aim of this development was to animate the artificial lid in the orbita prosthesis to give the patient a much more natural appearance. All components in the prosthesis were integrated to create an artificial lid that would blink in synchrony with that of the healthy eye. The material which proved to be most suited for the moveable eyelid was cast latex milk. It was elastic, would take dyes and was robust enough to withstand approximately 30 involuntary lid movements per minute. The artificial upper lid was pulled up behind the eye prosthesis by means of a fine thread, analogous to the natural lid opener. This is driven by a DC micromotor which lifts the upper lid in a cranial direction with a polyamid thread attached to the reinforced rim of the lid. The thread was wound onto a minute pulley. After a successful model had been constructed, an electronic circuit was developed in SMD (Surface Mounted Device) technique which drove the motor and processed the muscle potential necessary for the synchronization. These two double-sided circuit boards were positioned directly behind the artificial eye, which had been created specially by an ophthalmologist. By means of five integrated potentiometers, the muscle signals picked up were individually modified and adjusted to eliminate any delays in the lid movement. The low nominal capacity provided by accumulators ruled them out as a possible power supply for the electronics and motor, and instead, a small, light replaceable battery, capable of powering the motor for 7 to 14 days, was chosen. The individual components were then assembled and housed in a case of rigid acrylate plastic. It was possible to position the battery either under or behind the motor and to and stagger the electronics parts to the position of the battery and motor. This enhanced the adaptability of the case's geometric form to the individual orbit defect. Clinical tests with healthy test persons and patients with implant-anchored orbital prostheses demonstrated that muscle potentials from the orbicularis oculi muscle could be picked up from the healthy upper lid with bipolar needle electrodes. This was also possible in some cases when after exenteration the orbicularis oculi muscle remained partially active and continued to emit muscle potentials. With these biopotentials, the synchronic lid movement of the prototype was tested on a voluntary healthy test person. It functioned flawlessly. After extensive laboratory tests, two patients were rehabilitated with the new orbita prosthesis. For each patient a case for the components was designed and fitted into a silicone prosthesis retained with implant-anchored magnet abutments. The muscle potentials were conducted by an intramuscular electromyography (EMG) to trigger synchronous lid movement. With the first patient, a sterile needle electrode was used, but this had to be reinserted into the muscle each time the prosthesis was fitted. In the second patient the muscle potentials were picked up via a thin EMG-electrode implanted subcutaneously. In both cases bipolar conduction was taken. The second different electrode was attached to one implant-anchored magnet; the neutral electrode to another. In both patients, the muscle impulses emitted during lid closure initiated an artificial lid movement in synchrony with the healthy eyelid. Since the component parts cannot be reduced beyond a certain minimum size, not all orbit prosthesis wearers can be rehabilitated with the new prosthesis. In order to fit patients with smaller defects, future research will have to concentrate on a further reduction in component size. With further developments in telemetric procedures it will become possible to transmit signals received from a EMG electrode implanted in the muscle to the prosthesis without the dangers of infection inherent in conducting them through the skin.

Neste trabalho foram estudadas as fases topológicas não triviais presentes em sistemas formados pela deposição de átomos de grafeno. Encontramos que quando um átomo hibridiza fortemente com o grafeno, apresenta um momento magnético e um forte spin-órbirta é possível a formação de uma rede hexagonal de baricentros que efetivamente gera uma estrutura de bandas característica de um efeito hall quântico anômalo. Especificamente, determinamos que o Ru satisfaz estas características. Quando este metal é depositado em uma configuração triangular no grafeno ocorrem picos na densidade de estados localizados no centro geométrico (baricentro) dos triângulos formados pelos Ru. Estes picos estão distribuídos de forma hexagonal e efetivamente geram uma estrutura de bandas que nas proximidades do nível de Fermi apresenta uma configuração de spin característica do efeito Hall quântico anômalo. Adicionalmente, encontramos que o sistema composto pela absorção de Ba ou Sr no grafeno favorece a formação do efeito Hall quântico de spin. Neste sistema, o acoplamento spin-órbita (SOC) gera um gap mais de 1000 vezes maior ao período no grafeno prístino. Para o estudo destes sistemas, implementamos no código SIESTA a aproximação on-site do acoplamento spin-órbita via o formalismo dos pseudopotenciais relativísticos de norma conservada. Nossa implementação foi testada a partir do estudo de fenômenos já conhecidos: i) o strong spin-splitting gerado no grafeno pela adsorção de Au, ii) o efeito hall quântico de spin no poço quântico de HgTe/CdTe e, iii) a formação de estados topológicos na superfície do Bi2Se3 e as fases magnéticas deste material com átomos de Mn adsorvidos. / In this work, were studied the non-trivial topological phases present in systems formed by deposition of atoms in graphene. We found that when an atom hybridizes strongly with grapheme, has a magnetic moment and a strong spin-orbit it is possible the formation of a hexagonal network of barycentres that effectively generates a structure band characteristic of a quantum anomalous Hall effect. Specifically, we determined that Ru satisfies these characteristics. When this metal is deposited in a triangular configuration in grapheme, peaks occur in the density of localized states in the geometric center (centroid) of the triangles formed by Ru. These peaks are distributed in a hexagonal structure and effectively generates a band structure that near the Fermi level has a spin configuration characteristic of the spin quantum Hall effect anomalous. Additionally, we found that the system composed by the adsorption of Ba or Sr in grapheme, promotes the formation of spin quantum Hall effect. In this system, the spin-orbit coupling (SOC) generates a gap more than 1000 times grater that predicted in pristine praphene. To study these systems, wu implemented in the code SIESTA the on-site approach of the spin-orbit coupling throught the formalism of norm conserved relativistic pseudo potentials. Our implementation was tested from the study of phenomena already known: i) the strong spin-splitting generated in graphene by adsorption of Au, ii) the quantum spin Hall effect in quantum well of HgTe / CdTe and, iii) formation of topological states in the surface of Bi2Se3 and the magnetic of this material with Mn atoms adsorved.

<div>As destinations of missions in both human and robotic spaceflight become more exotic, a foundational understanding the dynamical structures in the gravitational environments enable more informed mission trajectory designs. One particular type of structure, quasi-periodic orbits, are examined in this investigation. Specifically, efficient computation of quasi-periodic orbits and leveraging quasi-periodic orbits as trajectory design alternatives in the Earth-Moon and Sun-Earth systems. First, periodic orbits and their associated center manifold are discussed to provide the background for the existence of quasi-periodic motion on n-dimensional invariant tori, where n corresponds to the number of fundamental frequencies that define the motion. Single and multiple shooting differential corrections strategies are summarized to compute families 2-dimensional tori in the Circular Restricted Three-Body Problem (CR3BP) using a stroboscopic mapping technique, originally developed by Howell and Olikara. Three types of quasi-periodic orbit families are presented: constant energy, constant frequency ratio, and constant mapping time families. Stability of quasi-periodic orbits is summarized and characterized with a single stability index quantity. For unstable quasi-periodic orbits, hyperbolic manifolds are computed from the differential of a discretized invariant curve. The use of quasi-periodic orbits is also demonstrated for destination orbits and transfer trajectories. Quasi-DROs are examined in the CR3BP and the Sun-Earth-Moon ephemeris model to achieve constant line of sight with Earth and avoid lunar eclipsing by exploiting orbital resonance. Arcs from quasi-periodic orbits are leveraged to provide an initial guess for transfer trajectory design between a planar Lyapunov orbit and an unstable halo orbit in the Earth-Moon system. Additionally, quasi-periodic trajectory arcs are exploited for transfer trajectory initial guesses between nearly stable periodic orbits in the Earth-Moon system. Lastly, stable hyperbolic manifolds from a Sun-Earth L₁ quasi-vertical orbit are employed to design maneuver-free transfer from the LEO vicinity to a quasi-vertical orbit.</div>

Submitted by Ricardo Cedraz Duque Moliterno (ricardo.moliterno@uefs.br) on 2015-10-01T23:29:45Z No. of bitstreams: 1 Aspergillus terreus isolamento identifica??o e avalia??o da capacidade catalitica na redu??o de cetonas pr? quirais.pdf: 1820055 bytes, checksum: c5c60d2c4b1c577c84c8b1baaa95660d (MD5) / Made available in DSpace on 2015-10-01T23:29:45Z (GMT). No. of bitstreams: 1 Aspergillus terreus isolamento identifica??o e avalia??o da capacidade catalitica na redu??o de cetonas pr? quirais.pdf: 1820055 bytes, checksum: c5c60d2c4b1c577c84c8b1baaa95660d (MD5) Previous issue date: 2014-09-30 / The object of this inquiry is the isolation, the selection and the potential evaluation of a microorganism with biocatalytic activity in carrying out selective-stereo biorreduction of pro-chial ketones. In the research procedure, Fungi was isolated from soil samples contaminated with lead. Only one of the isolates fungi, identified as Aspergillus terreus, presented good catalytic activity in the reduction of acetophenone. The biomass was grown submerged in broth culture, inoculated with 1,1 x 103 (spores/mL of malt extract) and maintained at 30?C under orbital agitation. Morphological differences and catalytic activity were evaluated in function of the orbit of agitation during the growth process. The catalytic activity in terms of conversion of acetophenone and enantiomeric excess (S), ee_S, in 1-feniletanol, was determinate in conjunction with the growth curve of the fungus. The results were used to construct a graphic showing the variation of quality of the catalyst, according to age of biomass. Apart from acetophenone were tested o-Xacetophenone, p-Xacetophenone and m-Xacetophenone (X = methyl, methoxy, nitro, fluorine, bromine). For reaction with 24 hours growing cells (30?C; 150rpm/r = 50mm), the conversions were between 27% and 97% with ee_S between 41% and 83%. For reactions with cells in suspension in buffered medium (pH = 4.5 ? 6,5) was decrease in activity/selectivity at pH above 5.5. The kinetics of conversion was evaluated for biomasses with different ages and for various concentrations of acetophenone. An amount between 100mg and 200mg of biomass (dry mass) with 168 hours of culture can convert 100mg of acetophenone to 1(S)-feniletanou ee_S (91%) with 98% yield in 72 hours of reaction (93% at 48 hours). The development of this process described above, constitutes the body of this thesis. / O objetivo desta pesquisa ? o isolamento, a sele??o e a avalia??o de um microorganismo com atividade biocatalisadora na biorredu??o estereoseletiva de cetonas pro-quirais. No procedimento de investiga??o, fungos foram isolados de amostras de solo contaminadas com chumbo. Apenas um dos fungos isolados, identificado geneticamente como Aspergillus terreus, apresentou boa atividade catal?tica na redu??o de acetofenona. A biomassa foi cultivada submersa no caldo de cultura, inoculado com 1,1x103 (esporos/mL de extrato de malte) e mantido a 30? sob agita??o orbital. Diferen?as morfol?gicas e de atividade catal?tica foram avaliadas em fun??o da ?rbita de agita??o durante o crescimento. A atividade catal?tica, em termos de convers?o da acetofenona e do excesso enantiom?rico (S), ee_S, no 1-feniletanol, foi determinada em conjunto com a curva de crescimento do fungo. Os resultados foram usados para construir um gr?fico mostrando a varia??o da qualidade do catalisador em fun??o da idade da biomassa. Al?m de acetofenona, foram testadas o-Xacetofenona, p-Xacetofenona e m-Xacetofenona (X=metil, metoxi, nitro, fl?or, bromo). Para 24 horas de rea??o com c?lulas em crescimento (30?C; 150rpm/r = 50mm), as convers?es ficaram entre 94 e 100%, com ee_S ? 98% para acetofenona e para acetofenonas orta ou meta substitu?das. Com substituintes na posi??o para, a convers?o ficou entre 27% e 97%, com ee_S entre 41% e 83%. Para rea??es com c?lulas em suspens?o em meio tamponado (pH = 4,5 ? 6,5), houve queda na atividade/seletividade em pH acima de 5,5. A cin?tica de convers?o foi avaliada para biomassas com idades distintas e para v?rias concentra??es de acetofenona. Uma quantidade entre 100mg e 200mg de biomassa (massa seca) com 168 horas de cultura, pode converter 100mg de acetofenona a 1(S)-feniletanol (ee_S 91%), com 98% de rendimento em 72 horas de rea??o (93% em 48 horas). O desenvolvimento desse processo, acima descrito, constitui o corpo desta Tese.

<p>The main focus of this thesis is the investigation of the dissociation dynamics of aryl halides using femtosecond pump-probe spectroscopy. In the monohalogenated aryl halides, iodo-, bromo- and chlorobenzene, the rate of dissociation following excitation at 266 nm in the gas phase increased with increasing mass of the halogen atom. This process was assigned to predissociation of the initially excited singlet (π, π*) state via a repulsive triplet (n, σ*) state due to spin-orbit interaction. In addition to the predissociative mechanism, a direct dissociation channel was observed in iodobenzene. The rate of the predissociation in bromobenzene was found to be faster in the condensed phase than in the gas phase, which can be explained by solvent-induced symmetry perturbations. <i>Ab initio</i> calculations of the potential energy surfaces of the ground state and several low lying excited states in bromobenzene have been performed in order to verify the suggested mechanism. Substituting one of the hydrogen atoms in bromobenzene affected the predissociation rate significantly. In o-, m- and p-dibromobenzene the predissociation rate increased with decreasing distance between the bromine atoms in accordance with an increased spin-orbit interaction introduced by the bromine substituent. The fastest predissociation rate was observed in 1,3,5-tribromobenzene. With chlorine and fluorine substitution, inductive and conjugative effects were found to be of importance. In the o- and m-isomers of the dihalogenated aryl halides, an additional faster dissociation channel was observed. Guided by <i>ab initio</i> calculations of the potential energy surfaces in the dibromobenzene isomers, we ascribed the fast dissociation pathway to predissociation of an initially excited triplet state. Upon methyl group substitution in bromobenzene, the decreased lifetime of the initially excited state was attributed to an incresaed density of coupled states.</p><p>Another system which has been studied in the condensed phase is diiodomethane. Using Car-Parrinello molecular dynamics simulations we observed a prompt dissociation and subsequent recombination to the isomer, iso-diiodomethane, in acetonitrile solution.</p><p>Vibrational wavepacket dynamics in the C (¹Σ⁺) state of NaK were studied using a direct ionization probing scheme. A simple analytical expression for the pump-probe signal was developed in order to see what factors that govern direct ionization of the vibrational wavepacket. Our experimental data was consistent with a photoionization transition dipole moment that varies with internuclear distance.</p>

The main focus of this thesis is the investigation of the dissociation dynamics of aryl halides using femtosecond pump-probe spectroscopy. In the monohalogenated aryl halides, iodo-, bromo- and chlorobenzene, the rate of dissociation following excitation at 266 nm in the gas phase increased with increasing mass of the halogen atom. This process was assigned to predissociation of the initially excited singlet (π, π*) state via a repulsive triplet (n, σ*) state due to spin-orbit interaction. In addition to the predissociative mechanism, a direct dissociation channel was observed in iodobenzene. The rate of the predissociation in bromobenzene was found to be faster in the condensed phase than in the gas phase, which can be explained by solvent-induced symmetry perturbations. Ab initio calculations of the potential energy surfaces of the ground state and several low lying excited states in bromobenzene have been performed in order to verify the suggested mechanism. Substituting one of the hydrogen atoms in bromobenzene affected the predissociation rate significantly. In o-, m- and p-dibromobenzene the predissociation rate increased with decreasing distance between the bromine atoms in accordance with an increased spin-orbit interaction introduced by the bromine substituent. The fastest predissociation rate was observed in 1,3,5-tribromobenzene. With chlorine and fluorine substitution, inductive and conjugative effects were found to be of importance. In the o- and m-isomers of the dihalogenated aryl halides, an additional faster dissociation channel was observed. Guided by ab initio calculations of the potential energy surfaces in the dibromobenzene isomers, we ascribed the fast dissociation pathway to predissociation of an initially excited triplet state. Upon methyl group substitution in bromobenzene, the decreased lifetime of the initially excited state was attributed to an incresaed density of coupled states. Another system which has been studied in the condensed phase is diiodomethane. Using Car-Parrinello molecular dynamics simulations we observed a prompt dissociation and subsequent recombination to the isomer, iso-diiodomethane, in acetonitrile solution. Vibrational wavepacket dynamics in the C (1Σ+) state of NaK were studied using a direct ionization probing scheme. A simple analytical expression for the pump-probe signal was developed in order to see what factors that govern direct ionization of the vibrational wavepacket. Our experimental data was consistent with a photoionization transition dipole moment that varies with internuclear distance.

This work comprises two main parts. The first part outlines our efforts to expand on the recent work of Gütlich et.al. by synthesizing Co(II) based spin crossover systems within a dendritic framework. We wanted to investigate the possibility of synthesizing different first generation, triazole containing dendrimers using “click” type reactions and their coordination ability with Co(II) ions. To this end we have had limited success mainly due to the numerous challenges in synthesizing a pure dendrimer product. The second part details our efforts in the synthesis of a mononuclear Co(II) based single molecule magnet. This comes as an extension to recent reports by Chang and Long where they have successfully obtained mononuclear Fe(II) single molecule magnets by inducing structural distortions within the complexes to amplify the spin-orbit coupling. We postulated that the use of Co(II) in conjunction with a bulky ligand framework would lead to desirable magnetic properties. We chose the known bis(imino)pyridine ligand scaffold due to its rich chemistry and its interesting and unexpected coordination behaviour, as we have seen in previous research efforts by our lab. To this end we were successful in isolating and characterizing 4 compounds, and we have carried out detailed magnetic measurements on the two most magnetically interesting species.

This work comprises two main parts. The first part outlines our efforts to expand on the recent work of Gütlich et.al. by synthesizing Co(II) based spin crossover systems within a dendritic framework. We wanted to investigate the possibility of synthesizing different first generation, triazole containing dendrimers using “click” type reactions and their coordination ability with Co(II) ions. To this end we have had limited success mainly due to the numerous challenges in synthesizing a pure dendrimer product. The second part details our efforts in the synthesis of a mononuclear Co(II) based single molecule magnet. This comes as an extension to recent reports by Chang and Long where they have successfully obtained mononuclear Fe(II) single molecule magnets by inducing structural distortions within the complexes to amplify the spin-orbit coupling. We postulated that the use of Co(II) in conjunction with a bulky ligand framework would lead to desirable magnetic properties. We chose the known bis(imino)pyridine ligand scaffold due to its rich chemistry and its interesting and unexpected coordination behaviour, as we have seen in previous research efforts by our lab. To this end we were successful in isolating and characterizing 4 compounds, and we have carried out detailed magnetic measurements on the two most magnetically interesting species.

No description available.