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In dieser Arbeit wird durch Modellrechnungen gezeigt, wie die Stickstoffinversion in Azacyclen als molekularer Schalter genutzt werden könnte. Hierzu werden ein Fluorazetidin- und ein Fluorazacyclopentanderviat quantenchemisch untersucht. Das letztere Molekül wird auch quantendynamisch untersucht. Jedes der beiden Moleküle besitzt zwei stabile Konformationen. Es wird gezeigt, dass das Azabicyclopentanderivat von der einen Konformation mittels zweier linear polarisierter IR-Laserpulse durch sogenanntes “ladder climbing” in die andere überführt werden kann. / In this work it is shown by model simulation, how the nitrogon inversion in azacycles could be used as a molecular switch. For this a azetidine derivative and a fluoroazabicyclopentane derivative have been investigated quantumchemically. Both of the molecules have two stable conformers. The latter molecule is also investigated quantumdynamically. Its is shown that the azabicyclopentanederivative can be switched from one conformer to the other by using two linear polarised IR laser pulses via ladder climbing.

The use of optical fiber sensors is increasing widely in industry, civil, medicine, defense and research. Among different categories of these sensors is the Extrinsic Fabry-Perot interferometer (EFPI) sensor which is inherently simple and requires only modest amount of interface electronics. These advantages make it suitable for many practical applications. Investigating a cost-effective, reliable and repeatable method for optical fiber sensor fabrication is challenging work. In this thesis, a system for controlled fabrication of Fabry-Perot optical fiber sensors is developed and presented as the first attempt for the long-term goal of automated EFPI sensor fabrication. The sensor fabrication control system presented here implements a real-time control of a carbon dioxide (CO₂) laser as sensor bonding power, an optical fiber white light interferometric subsystem for real-time monitoring and measurement of the air gap separation in the Fabry-Perot sensor probe, and real-time control of a piezoelectric (PZT) motion subsystem for sensor alignment. The design of optoelectronic hardware and computer software is included. A large number of sensors are fabricated using this system and are tested under high temperature and high pressure. This system as a prototype system shows the potential in automated sensor fabrication. / Master of Science

Mais recentemente foi proposta uma nova técnica para tratamento de doenças relacionadas à retina humana, utilizando descargas laser na retina com seqüência de pulsos da ordem de 200 \'mü\'s, em substituição ao tratamento convencional que utiliza pulsos longos da ordem de 300 ms. A principal vantagem da nova técnica é a preservação (sem morte celular) do tecido exposto ao laser. Esse trabalho apresenta os mecanismos adotados para o desenvolvimento de um sistema eletrônico de controle de uma cavidade laser em 586 nm, para uso oftalmológico, que objetiva atender o protocolo exigido por essa técnica mais recente. O referido protocolo exige a formação de pulsos rápidos de laser, o que torna vital a velocidade do sistema eletrônico de controle da cavidade laser. Para atender os requisitos do projeto foram implementados dois controladores de corrente em malha fechada PI (Proporcional integrative controller) que trabalham em sincronismo, um controlador de potência óptica em malha fechada PI, e circuitos auxiliares de controle térmico da cavidade laser. Em software foram implementados um PI de potência, com objetivo de tornar a malha de controle estável com o tempo de resposta necessário, e o PI de controle térmico dos elementos da cavidade laser. Os testes realizados do protótipo demonstraram que o sistema de controle atendeu as especificações de projeto, principalmente no que se refere a tempo de resposta do pulso rápido, ponto fundamental na obtenção do protocolo clínico (FastPulse), que esse trabalho objetiva atender. Adicionalmente, o protótipo foi submetido a teste clínico em um paciente, e os resultados demonstraram eficácia no tratamento e ausência de marcas (lesões) na retina. / Recently, scientists have proposed a new technique for treating diseases related to the human retina, which is based on retinal laser discharges using pulse sequence around of 200 \'mü\'s, replacing the conventional treatment using long pulses around of 300 ms. The main advantage of the new technique is the conservation (without cell death) of the area exposed to the laser. This work presents the mechanisms adopted for the development of an electronic control system of a laser cavity at 586 nm for ophthalmic use, which aims to meet the protocol required by this recent technique. The protocol requires the formation of rapid pulses of laser, which makes the electronic control system response velocity of the laser cavity vital to the protocol. To meet the project requirements were implemented two current controllers in closed loop PI (proportional integrative controller) working synchronized, an optical power controller in closed loop PI, and auxiliary circuits for temperature control of the laser cavity. Software were implemented for two controls, a PI power, in order to make the control loop stable with the required response time, and a PI thermal control for elements of the laser cavity. Tests showed that the prototype met the design specifications, especially regarding the response time of rapid pulse, key point in obtaining the clinical protocol (FastPulse), that this work aims to meet. Additionally, the prototype was subjected to clinical trial on a patient, and the results demonstrated efficacy and no visible lesions were noticed on retina.

Mais recentemente foi proposta uma nova técnica para tratamento de doenças relacionadas à retina humana, utilizando descargas laser na retina com seqüência de pulsos da ordem de 200 \'mü\'s, em substituição ao tratamento convencional que utiliza pulsos longos da ordem de 300 ms. A principal vantagem da nova técnica é a preservação (sem morte celular) do tecido exposto ao laser. Esse trabalho apresenta os mecanismos adotados para o desenvolvimento de um sistema eletrônico de controle de uma cavidade laser em 586 nm, para uso oftalmológico, que objetiva atender o protocolo exigido por essa técnica mais recente. O referido protocolo exige a formação de pulsos rápidos de laser, o que torna vital a velocidade do sistema eletrônico de controle da cavidade laser. Para atender os requisitos do projeto foram implementados dois controladores de corrente em malha fechada PI (Proporcional integrative controller) que trabalham em sincronismo, um controlador de potência óptica em malha fechada PI, e circuitos auxiliares de controle térmico da cavidade laser. Em software foram implementados um PI de potência, com objetivo de tornar a malha de controle estável com o tempo de resposta necessário, e o PI de controle térmico dos elementos da cavidade laser. Os testes realizados do protótipo demonstraram que o sistema de controle atendeu as especificações de projeto, principalmente no que se refere a tempo de resposta do pulso rápido, ponto fundamental na obtenção do protocolo clínico (FastPulse), que esse trabalho objetiva atender. Adicionalmente, o protótipo foi submetido a teste clínico em um paciente, e os resultados demonstraram eficácia no tratamento e ausência de marcas (lesões) na retina. / Recently, scientists have proposed a new technique for treating diseases related to the human retina, which is based on retinal laser discharges using pulse sequence around of 200 \'mü\'s, replacing the conventional treatment using long pulses around of 300 ms. The main advantage of the new technique is the conservation (without cell death) of the area exposed to the laser. This work presents the mechanisms adopted for the development of an electronic control system of a laser cavity at 586 nm for ophthalmic use, which aims to meet the protocol required by this recent technique. The protocol requires the formation of rapid pulses of laser, which makes the electronic control system response velocity of the laser cavity vital to the protocol. To meet the project requirements were implemented two current controllers in closed loop PI (proportional integrative controller) working synchronized, an optical power controller in closed loop PI, and auxiliary circuits for temperature control of the laser cavity. Software were implemented for two controls, a PI power, in order to make the control loop stable with the required response time, and a PI thermal control for elements of the laser cavity. Tests showed that the prototype met the design specifications, especially regarding the response time of rapid pulse, key point in obtaining the clinical protocol (FastPulse), that this work aims to meet. Additionally, the prototype was subjected to clinical trial on a patient, and the results demonstrated efficacy and no visible lesions were noticed on retina.

Cette thèse porte sur la description théorique de processus dynamiques ultra-rapides de molécules polyatomiques et de leur contrôle par impulsions laser. Nous avons d’abord étudié la photochimie de l’aniline à l’aide de calculs de structure électronique. Nous avons d´écrit plusieurs régions clé des surfaces d’énergie potentielle et analysé ces résultats en relation avec les données expérimentales existantes. La photochimie de la pyrazine a été étudiée par des calculs de dynamiques quantique basés sur un Hamiltonien modèle incluant les quatre états électroniques excités de plus basse énergie et seize modes de vibration. Nous montrons que l’état sombre Au(nπ∗) joue un rôle important dans la dynamique de la molécule après photo-excitation. Un modèle simplifié à deux états et quatre modes a été utilisé pour étudier le contrôle par laser de la dynamique de la pyrazine photo-excitée. Nous proposons un mécanisme visant à augmenter la durée de vie de l’état B2u(ππ∗) en utilisant l’effet Stark induit par une impulsion laser intense non-résonante. / The central subject of this thesis is the theoretical description of ultrafast dynamical processes in molecular systems of chemical interest and of their control by laser pulses. We first use electronic structure calculations to study the photochemistry of aniline. A umber of previously unknown features of the potential energy surfaces of the low-lying elec-tronic states are reported, and analyzed in relation with the experimental results available. We use quantum dynamics simulations, based on a model Hamiltonian including the four lowest excited electronic states and sixteen vibrational modes, to investigate the photochem-istry of pyrazine. We show that the dark Au(nπ∗) state plays an important role in the ultrafast dynamics of the molecule after photoexcitation. The laser control of the excited state dynamics of pyrazine is studied using a simplified two-state four-mode model Hamiltonian. We propose a control mechanism to enhance the lifetime of the bright B2u(ππ∗) state using the Stark effect induced by a strong non-resonant laser pulse. We finally focus on the laser control of the tunneling dynamics of the NHD2 molecule, using accurate full-dimensional potential energy and dipole moment surfaces. We use simple effective Hamiltonians to explore the effect of the laser parameters on the dynamics and design suitable laser fields to achieve the control. These laser fields are then used in MCTDH quantum dynamics simulations. Both enhancement and suppression of tunneling are achieved in our model.