Por sua disponibilidade e características diferenciadas, a madeira foi um dos primeiros materiais a ser usado pelos seres humanos, com uma grande multiplicidade de usos, diretos e indiretos. Ainda hoje é uma importante fonte de energia doméstica e industrial, além de ser usada como matéria prima na fabricação de papel e celulose, nas indústrias químicas, moveleira, naval, de artigos esportivos, brinquedos e instrumentos musicais, bem como na construção civil e na distribuição de energia elétrica. A madeira tem sido bastante estudada, sendo do conhecimento dos pesquisadores da área, a influência de vários fatores no desenvolvimento das árvores e por consequência, nas madeiras, como temperatura, latitude, longitude, altitude, insolação, solo e índice pluviométrico, razões pelas quais, quando se trata de madeira, se fala sempre em propriedades médias. A densidade é na opinião da grande maioria dos pesquisadores, a propriedade mais importante da madeira, por manter estreitas relações com propriedades físicas e mecânicas. Há três tipos de densidades, básica, aparente e a verde. Destas, usou-se a densidade aparente, a 12% de umidade e próxima da umidade de equilíbrio com o meio ambiente e a densidade a verde, na simulação no laboratório. Neste trabalho foram utilizadas madeiras de densidades variáveis, de sete espécies diferentes, a saber: freijó, peroba-mica, jequitibá, muiracatiara, cumaru, ipê e sucupira. Para a determinação das densidades pelo método não convencional, um dos objetivos deste trabalho, foi usar os radioisótopos: 241Am, 133Ba, 192Ir, 137Cs e 60Co, um detetor de cintilação de NaI e um espectrômetro multicanal, desenvolvendo-se uma técnica alternativa, rápida e precisa, fato evidenciado pelos resultados obtidos. Os parâmetros nucleares obtidos, como meias espessuras e coeficientes de absorção linear, proporcionaram a escolha do radioisótopo, 137Cs, em relação à energia, atividade, espessuras ótimas de ensaio, resolução e proteção radiológica, para simulação em laboratório da integridade física de postes de madeira e árvores vivas, constituindo os parâmetros nucleares e as simulações em laboratório, os outros importantes objetivos do trabalho. / Due to availability and differentiated features, wood was one of first materials to be used by humans, with a wide variety of applications. Today it is still an important source of domestic and industrial energy, besides to be used as raw material in manufacture of pulp and cellulose, in chemical industry, furniture, naval, sporting goods, toys and musical instruments as well as in construction and distribution of electric energy. Wood has been studied intensively and researchers in the area are aware of the influence of various factors in the development of trees and as consequence, in wood, such as: temperature, latitude, longitude, altitude, sunlight, soil and rainfall, reasons for which when it refers to wood, always it is average properties. The density it is in the opinion of majority of researchers, the most important property of wood, maintaining a close relationship with mechanical and physics properties of wood. There are three types of densities; basic, apparent and green and among these we used the apparent density to 12% of moisture content and green, density of living trees. In this work it was used woods of various densities, of seven different species of trees, namely: ¨freijó¨, ¨peroba-mica¨, ¨jequitibá, muiracatiara, cumaru, ipê and sucupira. For the determination of densities, one of the goals of this work, was to use the radioisotopes: 241Am, 133Ba, 192Ir, 137Cs and 60Co, a NaI scintillation detector and a multichannel spectrometer, developing a non-conventional method, fast and accurate, evidenced by results. The nuclear parameters obtained such as, half value layers and linear attenuation coefficients provided the choice of the best radioisotope, 137Cs, for inspection of electric wooden poles and living trees in the laboratory simulations, are others important goals of this work.

Por sua disponibilidade e características diferenciadas, a madeira foi um dos primeiros materiais a ser usado pelos seres humanos, com uma grande multiplicidade de usos, diretos e indiretos. Ainda hoje é uma importante fonte de energia doméstica e industrial, além de ser usada como matéria prima na fabricação de papel e celulose, nas indústrias químicas, moveleira, naval, de artigos esportivos, brinquedos e instrumentos musicais, bem como na construção civil e na distribuição de energia elétrica. A madeira tem sido bastante estudada, sendo do conhecimento dos pesquisadores da área, a influência de vários fatores no desenvolvimento das árvores e por consequência, nas madeiras, como temperatura, latitude, longitude, altitude, insolação, solo e índice pluviométrico, razões pelas quais, quando se trata de madeira, se fala sempre em propriedades médias. A densidade é na opinião da grande maioria dos pesquisadores, a propriedade mais importante da madeira, por manter estreitas relações com propriedades físicas e mecânicas. Há três tipos de densidades, básica, aparente e a verde. Destas, usou-se a densidade aparente, a 12% de umidade e próxima da umidade de equilíbrio com o meio ambiente e a densidade a verde, na simulação no laboratório. Neste trabalho foram utilizadas madeiras de densidades variáveis, de sete espécies diferentes, a saber: freijó, peroba-mica, jequitibá, muiracatiara, cumaru, ipê e sucupira. Para a determinação das densidades pelo método não convencional, um dos objetivos deste trabalho, foi usar os radioisótopos: 241Am, 133Ba, 192Ir, 137Cs e 60Co, um detetor de cintilação de NaI e um espectrômetro multicanal, desenvolvendo-se uma técnica alternativa, rápida e precisa, fato evidenciado pelos resultados obtidos. Os parâmetros nucleares obtidos, como meias espessuras e coeficientes de absorção linear, proporcionaram a escolha do radioisótopo, 137Cs, em relação à energia, atividade, espessuras ótimas de ensaio, resolução e proteção radiológica, para simulação em laboratório da integridade física de postes de madeira e árvores vivas, constituindo os parâmetros nucleares e as simulações em laboratório, os outros importantes objetivos do trabalho. / Due to availability and differentiated features, wood was one of first materials to be used by humans, with a wide variety of applications. Today it is still an important source of domestic and industrial energy, besides to be used as raw material in manufacture of pulp and cellulose, in chemical industry, furniture, naval, sporting goods, toys and musical instruments as well as in construction and distribution of electric energy. Wood has been studied intensively and researchers in the area are aware of the influence of various factors in the development of trees and as consequence, in wood, such as: temperature, latitude, longitude, altitude, sunlight, soil and rainfall, reasons for which when it refers to wood, always it is average properties. The density it is in the opinion of majority of researchers, the most important property of wood, maintaining a close relationship with mechanical and physics properties of wood. There are three types of densities; basic, apparent and green and among these we used the apparent density to 12% of moisture content and green, density of living trees. In this work it was used woods of various densities, of seven different species of trees, namely: ¨freijó¨, ¨peroba-mica¨, ¨jequitibá, muiracatiara, cumaru, ipê and sucupira. For the determination of densities, one of the goals of this work, was to use the radioisotopes: 241Am, 133Ba, 192Ir, 137Cs and 60Co, a NaI scintillation detector and a multichannel spectrometer, developing a non-conventional method, fast and accurate, evidenced by results. The nuclear parameters obtained such as, half value layers and linear attenuation coefficients provided the choice of the best radioisotope, 137Cs, for inspection of electric wooden poles and living trees in the laboratory simulations, are others important goals of this work.

<p>The absorption properties of the Pt1 chromophore at room temperature have been studied. Stretch, bend and torsion parameters for Pt(II), P, C (type 1, 2 and 4) and H have been parameterized for use in the MM3 force field. Parameters were fitted to energies computed at the B3LYP level of theory. The parameterized model was used to perform molecular dynamics simulations at room temperature. This was done for several environments and for time periods of up to 200 ps. Absorption properties were computed for snapshots from the dynamics, from which average absorption spectra were created. A conformational broadening of around 40 nm was found in the theoretical spectra, which is in good agreement with experiments. Due to a lack of solvent-solute interactions and the use of a less extensive basis set, a systematic blue shift of 40 nm is evident in the computed spectra.</p>

The absorption properties of the Pt1 chromophore at room temperature have been studied. Stretch, bend and torsion parameters for Pt(II), P, C (type 1, 2 and 4) and H have been parameterized for use in the MM3 force field. Parameters were fitted to energies computed at the B3LYP level of theory. The parameterized model was used to perform molecular dynamics simulations at room temperature. This was done for several environments and for time periods of up to 200 ps. Absorption properties were computed for snapshots from the dynamics, from which average absorption spectra were created. A conformational broadening of around 40 nm was found in the theoretical spectra, which is in good agreement with experiments. Due to a lack of solvent-solute interactions and the use of a less extensive basis set, a systematic blue shift of 40 nm is evident in the computed spectra.

Dans ce travail, les propriétés optiques non linéaires de différentes nanostructures métalliques à base d’or et d’argent sont étudiées. En particulier, une attention particulière est portée à la nature cohérente ou incohérente de la réponse. Pour cela, la technique de la Génération du Second Harmonique (SHG) est employée. C’est en effet l’une des méthodes optiques non linéaires les plus simples pour mettre en évidence cette nature cohérente ou incohérente de la réponse. Les échantillons utilisés pour cette mise en évidence sont constitués d’une part par des films diélectriques dopés par des nanoparticules bimétalliques d’alliages du type AuAg de différentes fractions molaires en or pour la réponse incohérente et d’autre part par des réseaux de nanocylindres d’or de différentes tailles disposés selon trois configurations géométriques (carrée, hexagonale et aléatoire) sur un substrat pour la réponse cohérente. La majeure partie du travail est dévolue à l’étude de la propagation et du doublage de fréquence en régime de faisceaux gaussiens et impulsions courtes dans les films diélectriques dopés par des nanoparticules bimétalliques en raison de phénomènes supplémentaires observés simultanément à la conversion de fréquence : absorption et réfraction non linéaire, phase de Gouy... Par la méthode des franges de Maker, les valeurs absolues des composantes de la susceptibilité non linéaire d’ordre 2 de ces films sont mesurées puis les valeurs absolues de l’hyperpolarisabilité quadratique des nanoparticules sont estimées sur la base d’un modèle de réponse incohérente. Enfin, une étude préliminaire sur la génération de continuum de lumière est présentée. La nature cohérente de la réponse SHG est recherchée dans les réseaux de nanocylindres. Nous montrons que l’origine de la réponse est associée à l’existence de défauts de surface dans ces nanostructures et donc conserve un caractère incohérent. Toutefois, nous avons pu mettre en évidence des effets associés à la taille des nanocylindres et à l’organisation des nanocylindres sur le substrat, ce dernier effet étant attaché à un caractère cohérent de la réponse / In this work, the non linear optical properties of different silver and gold metallic nanostructures are studied. In particular, a special attention is concerning the coherent or incoherent nature of the response. For that purpose, the Second Harmonic Generation (SHG) technique is used. It is indeed one of the simplest non linear optical methods to underline the coherent or incoherent nature of the response. Samples used for this reason are constituted on the first hand by dielectric films doped by bimetallic nanoparticles of clusters of the type AuAg of various gold molar fractions for the incoherent responses and on the other hand by arrays of gold nanocylinders of various sizes arranged according to three geometrical configurations (square, hexagonal and random) on a substrate for the coherent response. The major part of the work is devoted to the study of the propagation and the second harmonic frequency in regime of Gaussian beams and short pulses in dielectric films doped by bimetallic nanoparticles because of supplementary phenomena observed simultaneously in the conversion of frequency: non linear absorption and refraction, Gouy phase... By the method of the fringes of Maker, the absolute values of the coefficient of the second order non linear susceptibility of these films are measured then the absolute values of the quadratic hyperpolarizability of nanoparticles are estimated on the basis of a model of incoherent responses. Finally, a preliminary study on the light continuum generation is presented. The coherent nature of the SHG response is studied in the nanocylinders arrays. We show that the origin of the response is associated with the existence of the surface defects in these nanostructures and thus have an incoherent character. However, we were able to put in evidence the effects associated with the size of nanocylinders and with the organization of nanocylinders on the substrate, this last effect being attached to a coherent character of the response

Plants and bacteria both have specialized light-harvesting pigment-protein complexes, composed of a network of chromophores encompassed by a protein scaffold, that are involved in photosynthesis. While chromophore, as well as protein, composition and arrangement vary in these light-harvesting complexes, chromophores transfer energy as molecular excitation energy through their complex multi-chromophoric network with near perfect efficiency. Understanding the efficiency of this excitation energy transfer process has been the focus of many interdisciplinary studies. By elucidating the mechanisms involved in efficient excitation energy transfer in biological systems, we are able to guide the design of novel organic materials for their application in photovoltaic systems. Interdisciplinary studies of light-harvesting biological systems leverage advanced spectroscopic techniques and theoretical models to help explain the interaction be- tween excited electronic states. Difficulties in assigning the origin of spectral features in spectroscopy experiments arise from both homogeneous and inhomogeneous effects. Various computational studies have been able to provide theoretical models that help disentangle these effects and provide insight into the origin of some these spectral features. In this work, we present a computational approach that is used to calculate an ensemble of model Hamiltonians for a light-harvesting pigment-protein complex found in algae. To verify the reliability of our model, we compare various computed spec- tra with experimental measurements. Next, we extend our computational approach for parameterizing an ensemble of Hamiltonians for two configurationally unique or- ganic dimers. Finally, we examine the error of some of the approximations made while partitioning “system” and “bath” degrees of freedom when computing molecu- lar properties. Using these methods we are able to provide mechanistic interpretations and explanations of spectral signatures observed in various linear and nonlinear ex- perimental spectra.

A eficácia de métodos convencionais de transmissão, utilizados para medir absorção de materiais altamente transparentes, é geralmente limitada pela reflexão e espalhamento de luz. A espectroscopia de Lente Térmica, por outro lado, não é sensível a esses fenômenos, e tem sido amplamente usada na determinação de baixas absorções ópticas. Neste trabalho, estudamos uma configuração de Lente Térmica de duplo feixe (onda contínua cw), desenvolvida recentemente, e suas aplicações. Essa configuração otimiza a técnica de Lente Térmica, e aumenta significativamente a sensibilidade de medida. Foram realizados alguns cálculos computacionais e testes experimentais dessa configuração, e os resultados foram comparados com os de outra configuração, tradicionalmente utilizada, denominada de feixe duplo no modo-descasado. Várias aplicações foram feitas para líquidos e sólidos. Como resultado, obtivemos o espectro de absorção da água pura entre 350 e 528 nm, que indicou um valor mínimo de aproximadamente 1,5 &#8226 10-5 cm-1 em torno de 380 nm, que é mais baixo do que todos os valores da literatura. Coeficientes tão baixos quanto 2 &#8226 10-7 cm-1 podem ser medidos para a água, com 1W de potência, utilizando essa configuração otimizada. Estimamos um limite de detecção de ~ 6 &#8226 10-9 cm-1 (P = 1 W) para o solvente CCl4, que corresponde (até onde sabemos) ao menor valor já encontrado na literatura para líquidos, utilizando-se laser cw. Quanto à detecção de traços de impurezas, o limite para o Cr (III) em solução aquosa foi de ~ 40 ppb (ng/mL) em 514 nm, que corresponde a aproximadamente metade da concentração máxima ideal de Cr (III) em águas potáveis e naturais. Foram obtidos alguns resultados preliminares para a variação do caminho óptico com a temperatura (ds/dT), em sólidos com diferentes geometrias. Para a sílica fundida (quartzo vítreo) Suprasil, determinamos um limite superior para o coeficiente de absorção, cujos valores, 1 &#8226 10-6 cm-1 (em 493 nm) e 1 &#8226 10-5 cm-1 (em 355 nm), também são menores do que os resultados da literatura nessa região do espectro. A alta sensibilidade da técnica permitiu obter a absorção, em 1064 nm, das matrizes de materiais laser dopados com Nd3+, sendo (1,8 &#177 0,1) &#8226 10-3 cm-1 para o vidro Q-98 (Kigre), e (5 &#177 1 &#8226 10-4 cm-1 para o cristal Nd:YAG. Realizamos também medidas de eficiência quântica de fluorescência em nanocristais semicondutores (CdSe/ZnS) suspensos em THF e tolueno, com resultado aproximadamente 5 vezes mais preciso do que o obtido por técnica convencional de fluorescência. As principais vantagens da configuração otimizada, em relação à tradicional, são: um procedimento experimental simples, boa precisão nas medidas de difusividade térmica e, principalmente, a alta sensibilidade da técnica. As desvantagens são: um tempo de medida mais longo, e a necessidade de amostras maiores. / The efficiency of conventional transmission methods used to measure absorption of hightransparent materials is usually limited by light scattering and reflection. On the other hand, Thermal Lens spectroscopy is insensible to such phenomena and has been widely applied to determinate low optical absorptions. In this thesis, we have studied a recently developed dualbeam (continuous wave - cw) Thermal Lens configuration as well as its practical applications. This configuration optimizes the technique and significantly improves the measurement sensitivity. Some computational calculations and experimental tests of this approach were carried out. The results were compared with those obtained using a traditional configuration, named Mode-mismatched Dual-beam Thermal Lens. Several applications were made for liquids and solids. As a result, we obtained the absorption spectrum for pure water in the range of 350 to 528 nm, which indicated a minimal value of approximately 1,5 &#8226 10-5 cm-1 around 380 nm, that is lower than those found in literature. Absorption coefficients as small as 2 &#8226 10-7 cm-1, can be measured for water, using 1W of excitation power, with this optimized configuration. We have estimated a detection limit of ~ 6 &#8226 10-9 cm-1 (P = 1 W) for CCl4 solvent, which corresponds (to the best of our knowledge) to the smallest value found in the literature for liquids using cw laser. With regard to the chemical trace analysis, the detection limit was ~ 40 ppb (ng/mL) at 514 nm for Cr (III) in aqueous solutions, which is nearly half of the maximum desired Cr (III) concentration in drinking and natural waters. Some preliminary results for the temperature coefficient of the optical path length (ds/dT) were obtained at solids with different geometries. For the fused-silica (vitreous quartz) Suprasil, we have determined an upper limit for the absorption coefficient, whose values, 1 &#8226 10-6 cm-1 at 493 nm, and 1 &#8226 10-5 cm-1 at 355 nm, also are lower than the values found in literature in this spectrum region. The high sensitivity of the technique allowed us to measure the absorption (at 1064 nm) of matrices of Nd3+ doped laser materials: (1,8 &#177 0,1) &#8226 10-3 cm-1 for Q-98 glass (Kigre), and (5 &#177 1) &#8226 10-4 cm-1 for Nd:YAG crystal. We carried out as well measurements of fluorescence quantum yield of semiconductor nanocrystals (CdSe/ZnS) suspended in THF and toluene solvents, whose result was approximately 5 times more accurate than that obtained with the conventional fluorescence technique. The main advantages of the optimized configuration are: a simple experimental procedure, a good accuracy for thermal diffusivity measurements, and most important the high sensitivity of the technique. The drawbacks are: a longer time of measurements, and the requirement of larger samples.

In the field of second harmonic (SH) generation most studies have been concerned with maximizing conversion efficiencies, generally achievable at the phase matching (PM) condition. Outside of the PM the conversion efficiency drastically decreases. This has caused that the possible working conditions out of PM to remain largely unexplored. In this thesis work we initiated a systematic study of the SH behavior in under conditions of large phase mismatch. When a pump pulse crosses an interface between a linear and a nonlinear medium there are always two generated SH components. These components may be understood on the basis of the mathematical solution of the inhomogeneous wave equations at the SH frequency. The homogeneous (HOM) solution is a component with wave-vector k(2¿) as expected from the dispersion relation and exchanges energy with the pump until the inevitable walk-off. The inhomogeneous (INH) solution is a component with a wave-vector 2k(¿), twice the pump wave-vector, and travels locked to the pump pulse. We divide our work in two parts, one for each generated component. Inhomogeneous component. We start a systematic study of the behavior of the generated INH component, phase locked to the pump. The consequences of phase locking (PL) can guide us towards new scenarios by allowing working conditions hitherto assumed inaccessible for absorbing materials. We show that while the HOM component travels with the group velocity given by material dispersion, the IHN component is captured by the pump pulse and experiences the same effective dispersion of the pump. It does not follow the PM condition. It naturally follows that the suppression of absorption at the SH wavelengths will occur if the pump is tuned to a region of transparency. We extended the same theory for the generated third harmonic (TH). We then studied the surprising behavior of SH and TH INH components with frequencies above the absorption edge when the material is placed inside a cavity resonant only at the fundamental frequency. We have shown that the PL mechanism not only inhibits absorption but also fosters the enhancement of harmonic generation by several orders of magnitude compared to the no-cavity case. Finally, we tested the INH SH and TH behaviors in metallic frequency regime of material. Homogeneous component. The techniques used to PM the nonlinear interaction enable efficient nonlinear interactions but drastically limit the spectral bandwidth of the nonlinear optical process, making the designed frequency converter only suitable for a fixed input wavelength and single interaction only. It has been shown that the use of disordered nonlinear media relaxes the PM condition thus allowing one to achieve relatively efficient broad bandwidth regime of the frequency conversion. An example of a quadratic nonlinear medium with a disordered domain structure is an un-poled Strontium Barium Niobate (SBN) crystal. It is composed of a system of random size anti parallel ferroelectric domains that allow to phase-match any second-order parametric process over a broad range of wavelengths without any poling. We have initiated an experimental and theoretical investigation of the properties of the SH waves generated in SBN crystals, with an extension to the generated TH. This study covers the coherence and polarization properties of the generated signal, as well as its spatial distribution. In addition, we have made an experimental study of the noncollinear interaction of short optical pulses in a SBN crystal by using two fundamental waves intersecting inside the crystal. We have shown that this effect may be employed as a simple tool for monitoring both the pulse duration and initial chirp. This method offers a simple and economic alternative to the existing methods for pulse characterization.

A eficácia de métodos convencionais de transmissão, utilizados para medir absorção de materiais altamente transparentes, é geralmente limitada pela reflexão e espalhamento de luz. A espectroscopia de Lente Térmica, por outro lado, não é sensível a esses fenômenos, e tem sido amplamente usada na determinação de baixas absorções ópticas. Neste trabalho, estudamos uma configuração de Lente Térmica de duplo feixe (onda contínua cw), desenvolvida recentemente, e suas aplicações. Essa configuração otimiza a técnica de Lente Térmica, e aumenta significativamente a sensibilidade de medida. Foram realizados alguns cálculos computacionais e testes experimentais dessa configuração, e os resultados foram comparados com os de outra configuração, tradicionalmente utilizada, denominada de feixe duplo no modo-descasado. Várias aplicações foram feitas para líquidos e sólidos. Como resultado, obtivemos o espectro de absorção da água pura entre 350 e 528 nm, que indicou um valor mínimo de aproximadamente 1,5 &#8226 10-5 cm-1 em torno de 380 nm, que é mais baixo do que todos os valores da literatura. Coeficientes tão baixos quanto 2 &#8226 10-7 cm-1 podem ser medidos para a água, com 1W de potência, utilizando essa configuração otimizada. Estimamos um limite de detecção de ~ 6 &#8226 10-9 cm-1 (P = 1 W) para o solvente CCl4, que corresponde (até onde sabemos) ao menor valor já encontrado na literatura para líquidos, utilizando-se laser cw. Quanto à detecção de traços de impurezas, o limite para o Cr (III) em solução aquosa foi de ~ 40 ppb (ng/mL) em 514 nm, que corresponde a aproximadamente metade da concentração máxima ideal de Cr (III) em águas potáveis e naturais. Foram obtidos alguns resultados preliminares para a variação do caminho óptico com a temperatura (ds/dT), em sólidos com diferentes geometrias. Para a sílica fundida (quartzo vítreo) Suprasil, determinamos um limite superior para o coeficiente de absorção, cujos valores, 1 &#8226 10-6 cm-1 (em 493 nm) e 1 &#8226 10-5 cm-1 (em 355 nm), também são menores do que os resultados da literatura nessa região do espectro. A alta sensibilidade da técnica permitiu obter a absorção, em 1064 nm, das matrizes de materiais laser dopados com Nd3+, sendo (1,8 &#177 0,1) &#8226 10-3 cm-1 para o vidro Q-98 (Kigre), e (5 &#177 1 &#8226 10-4 cm-1 para o cristal Nd:YAG. Realizamos também medidas de eficiência quântica de fluorescência em nanocristais semicondutores (CdSe/ZnS) suspensos em THF e tolueno, com resultado aproximadamente 5 vezes mais preciso do que o obtido por técnica convencional de fluorescência. As principais vantagens da configuração otimizada, em relação à tradicional, são: um procedimento experimental simples, boa precisão nas medidas de difusividade térmica e, principalmente, a alta sensibilidade da técnica. As desvantagens são: um tempo de medida mais longo, e a necessidade de amostras maiores. / The efficiency of conventional transmission methods used to measure absorption of hightransparent materials is usually limited by light scattering and reflection. On the other hand, Thermal Lens spectroscopy is insensible to such phenomena and has been widely applied to determinate low optical absorptions. In this thesis, we have studied a recently developed dualbeam (continuous wave - cw) Thermal Lens configuration as well as its practical applications. This configuration optimizes the technique and significantly improves the measurement sensitivity. Some computational calculations and experimental tests of this approach were carried out. The results were compared with those obtained using a traditional configuration, named Mode-mismatched Dual-beam Thermal Lens. Several applications were made for liquids and solids. As a result, we obtained the absorption spectrum for pure water in the range of 350 to 528 nm, which indicated a minimal value of approximately 1,5 &#8226 10-5 cm-1 around 380 nm, that is lower than those found in literature. Absorption coefficients as small as 2 &#8226 10-7 cm-1, can be measured for water, using 1W of excitation power, with this optimized configuration. We have estimated a detection limit of ~ 6 &#8226 10-9 cm-1 (P = 1 W) for CCl4 solvent, which corresponds (to the best of our knowledge) to the smallest value found in the literature for liquids using cw laser. With regard to the chemical trace analysis, the detection limit was ~ 40 ppb (ng/mL) at 514 nm for Cr (III) in aqueous solutions, which is nearly half of the maximum desired Cr (III) concentration in drinking and natural waters. Some preliminary results for the temperature coefficient of the optical path length (ds/dT) were obtained at solids with different geometries. For the fused-silica (vitreous quartz) Suprasil, we have determined an upper limit for the absorption coefficient, whose values, 1 &#8226 10-6 cm-1 at 493 nm, and 1 &#8226 10-5 cm-1 at 355 nm, also are lower than the values found in literature in this spectrum region. The high sensitivity of the technique allowed us to measure the absorption (at 1064 nm) of matrices of Nd3+ doped laser materials: (1,8 &#177 0,1) &#8226 10-3 cm-1 for Q-98 glass (Kigre), and (5 &#177 1) &#8226 10-4 cm-1 for Nd:YAG crystal. We carried out as well measurements of fluorescence quantum yield of semiconductor nanocrystals (CdSe/ZnS) suspended in THF and toluene solvents, whose result was approximately 5 times more accurate than that obtained with the conventional fluorescence technique. The main advantages of the optimized configuration are: a simple experimental procedure, a good accuracy for thermal diffusivity measurements, and most important the high sensitivity of the technique. The drawbacks are: a longer time of measurements, and the requirement of larger samples.

Die vorliegende Arbeit verallgemeinert die Methode der Wellenpaketpropagation fuer isolierte molekulare Systeme auf molekulare Systeme mit Umgebungswechselwirkung. Im Rahmen der Dichtematrixtheorie werden am Beispiel des linearen Absorptionskoeffizienten und des Raman-Streuquerschnitts Ausdruecke fuer stationaere optische Funktionen abgeleitet. Diese Ausdruecke lassen sich als Fouriertransformation einer durch Dichtematrixpropagation erhaltenen Groesse verstehen, deren Dynamik auch durch die Umgebung des molekularen Systems beeinflusst wird. Am Beispiel von drei Modellsystemen (OH-Streckschwingung von Wasser, NO in Ar-Matrizen, HCl in Ar-Matrizen) wird der lineare Absorptionskoeffizient im infraroten und ultravioletten Spektralbereich berechnet. Die Ergebnisse werden mit experimentellen Daten verglichen. Aus der numerisch ansruchsvollen drei-dimensionalen Behandlung des HCl in Ar werden zusaetzlich Schluesse ueber die Dynamik des H-Atoms bei der Photodissoziation gezogen. Der Ausdruck fuer den Raman-Streuquerschnitt wird an einem theoretischen Modellsystem untersucht. Insbesondere wird die Temperatur- und Feldstaerkeabhaengigkeit des Spektrums diskutiert. / The well-known wave paket propagation method is extended from isolated molecular systems to molekular systems interacting with a dissipative environment. In the framework of density matrix theory formulations of stationary optical properties (linear absorption and Raman scattering cross section) are found. Essentially these formulations contain the Fourier-transform of a term given by density matrix propagation which is influenced by the environment. For three examples (OH stretching vibration in liquid water, NO in Ar-matrices, HCl in Ar-matrices) the linear absorption coefficient is calculated in the infrared and ultraviolett spectral range. Comparisons with experimental data are given. For the case of HCl in Ar-matrices additional information concerning the dynamics of the H-atom during the photodissociation is given. The Raman scattering cross section is calculated for a theoretical model system. Especially temperature dependence and the influence of the electric field strength on the spectra is discussed.