Neste trabalho, estudamos as propriedade ópticas da tetrapiridilporfirina (TPyP), usando clorofórmio como sol vente. Para a caracterização óptica linear foram medidos os espectros de fluorescência e absorbância, tendo este último nos permitido determinar a seção de choque para o estado fundamental com radiação incidente em 532 nm. Usamos a técnica de varredura Z com trem de pulsos (VZTP) para medirmos a absorção não linear da TPyP, em 532 nm, e determinamos, através de um modelo fenomenológico de cinco níveis, vários parâmetros espectroscópicos tais como seções de choques e tempos de vida dos estados. Além disso, com a utilização da técnica de espalhamento hiperRayleigh (HRS) medimos a primeira hiperpolarizabilidade da TPyP, dissolvida em clorofórmio em 1064 nm usando, como material de referência, a p-nitroanilina (PN A), diluída em metanol. / This work reports on the optical properties of the tetrakis(pyridil)porphyrin (TPyP). In order to perform the linear optical characterization, fluorescence and absorbance spectra were obtained, where the latter allowed the determination of the cross-section for the ground state with incident radiation at À = 532 nm. We used the Zscan tecnique with pulse trains (ZSPT) to measure the nonlinear absorption of TPyP, at 532 nm, and we managed to determine, through a phenomenological five levels model, several spectroscopic parameters such as cross-sections and lifetime of the states. Moreover, we measured the first hyperpolarizability of TPyP dissolved in chloroform, at À = 1064 nm, using the Hyper-Rayleigh scattering (HRS) technique. The reference material used for HRS measurements was p-nitroaniline (PNA) dissolved in methanol.

Magnetic fluid flow by thermomagnetic convection with and without buoyancy was studied in experiments and computational simulations. A mineral oil based ferro magnetic fluid was subjected to varying magnetic fields to induce thermomagnetic convection. As such fluids are mainly developed to increase heat transfer for cooling the fundamental effects on magnetic fluid flow was investigated using various magnetic field distributions. Computational simulations of natural and thermomagnetic convection are based on a Finite-Element technique and considered a constant magnetic field gradient, a realistic magnetic field generated by a permanent magnet and alternating magnetic fields. The magnetic field within the fluid domain was calculated by the magneto-static Maxwell equations and considered in an additional magnetic body force known as the Kelvin body force by numerical simulations. The computational model coupled the solutions of the magnetic field equations with the heat and fluid flow equations. Experiments to investigate thermomagnetic convection in the presence of terrestrial gravity used infrared thermography to record temperature fields that are validated by a corresponding numerical analysis. All configurations were chosen to investigate the response of the magnetic fluid to the applied body forces and their competition by varying the magnetic field intensity and its spatial distribution. As both body forces are temperature dependent, situations were analysed numerically and experimentally to give an indication of the degree by which heat transfer may be enhanced or reduced. Results demonstrate that the Kelvin body force can be much stronger than buoyancy and can induce convection where buoyancy is not able to. This was evident in a transition area if parts of a fluid domain are not fully magnetically saturated. Results for the transition from natural convection to thermomagnetic convection suggest that the domain of influence of the Kelvin body force is aligned with the dominance of the respective body force. To characterise the transition a body force ratio of the Kelvin body force to buoyancy was developed that identified the respective driving forces of the convection cells. The effects on heat transfer was quantified by the Nusselt number and a suitable Rayleigh number. A modified Rayleigh number was used when both body forces were active to define an effective body force by taking the relative orientation of both forces into account. Results for the alternating magnetic field presented flow fields that altered with the frequency of the applied magnetic field but with varying amplitude. This affected the heat transfer that alternated with the frequency but failed to respond instantaneously and a phase lag was observed which was characterised by three different time scales.

Nesta tese apresentamos uma extensão da técnica de espalhamento hiper-Rayleigh (HRS) e sua aplicação para o estudo dos mecanismos que interferem na primeira hiperpolarizabilidade molecular (). Utilizamos um laser Nd:YAG, Q-switched e mode-locked como bombeio para excitar as amostras. Este laser emite pulsos de 100 ps modulados por uma envoltória de Q-switch. A saída é uma seqüência de pulsos com intensidades que acompanham a forma da envoltória. Usamos este trem de pulsos para excitar as amostras na medida de espalhamento hiper-Rayleigh, e um sistema de detecção com resolução temporal suficiente para resolver cada pulso independentemente. Esta modalidade de bombeio permitiu eliminar o controle mecânico da intensidade, o que reduziu o tempo necessário para a medida e melhorou a estabilidade nas condições experimentais. O método com trem de pulsos proporciona meios de identificar contribuições luminescentes e evitar valores superestimados para a primeira hiperpolarizabilidade. Realizamos testes medindo a molécula de paranitroanilina em vários solventes e verificamos muito boa reprodutibilidade dos valores da literatura. Comparamos os resultados medidos com valores calculados a partir do método de Hartree-Fock e corrigimos o engrandecimento por ressonância utilizando um modelo de dois níveis. A comparação entre valores teóricos e experimentais teve uma diferença média de 15%. Um estudo análogo para a molécula de dianilina não reproduziu os valores experimentais e atribuímos a falha à inaplicabilidade do modelo de dois níveis para medidas no regime ressonante. Também estudamos a primeira hiperpolarizabilidade nas porfirinas TDMImP e TPPS4, sob a forma base livre e formando complexos com Zn2+, Fe3+ e Mn3+. Para a TPPS4 estendemos o estudo para observar os efeitos da protonação na base livre e da formação de oxo dímeros na FeTPPS4 e as alterações causadas pela presença de micelas de CTAB. A comparação direta entre os resultados é dificultada em muitos casos pela diferença no engrandecimento por ressonância. Foi possível verificar que a presença de micelas tem o efeito de diminuir o valor de na H2TPPS4 pH 7. As medidas de HRS em ambiente ácido (pH 4) corroboram com a literatura, indicando que a ocorre desprotonação na presença de micelas. Um estudo teórico e experimental dos três isômeros do aminofenol permitiu analisar os efeitos da posição relativa dos grupos radicais e do comprimento da conjugação sobre a primeira hiperpolarizabilidade. Verificamos que a alteração no caráter doador/aceitador para diferentes posições dos grupos radicais tem influência maior no valor de do que o comprimento da conjugação. Utilizamos compostos com o ligante salen, com grupos laterais etano e DR1 e com ligantes H2, Cu2+, Ni2+ e VO2+, para estudar como os diferentes grupos e complexos refletem diferenças no valor de . Foi possível verificar que diferentemente da absorção linear e da seção de choque para dois fótons, o ligante com grupos radicais DR1 causam um aumento na primeira hiperpolarizabilidade que é muito maior do que a soma das contribuições individuais. Os complexos têm primeiras hiperpolarizabilidades maiores do que o ligante com H2 e a comparação entre os dois grupos com diferentes radicais mostra que existe uma correlação entre os aumentos causados por diferentes complexos. / This thesis reports an extension of the Hyper-Rayleigh scattering technique (HRS) and its application to study the mechanisms that contribute to the molecular first hyperpolarizabilities (). We use a Nd:YAG laser, Q-switched and mode-locked, as pumping beam to excite the samples. The laser delivers 100 ps pulses modulated by a Q-switch envelope, and the output is a pulse sequence which intensities follow the shape of the envelope. This pulse train is used to excite the samples in a Hyper-Rayleigh scattering experiment and the signal for each mode-lock pulse is detected independently. This modality of pumping allows the removal of the mechanical intensity control, therefore reducing measurement time and improved experimental stability. The method with pulse train also provides means to identify luminescent contributions and avoid overestimated values for the first hyperpolarizability. We performed test measurements with para-nitroaniline in several solvents and verified very good reproducibility of literature values. We also compared the measured and calculated values, obtained with the Hartree-Fock method and corrected for resonance enhancement with a two level model. The comparison between theoretical and experimental values results in an average difference of 15%. Similar studies for the dianiline molecule failed to reproduce experimental values and we attributed the failure to the inadequacy of the of the two-level model to correct resonance enhancement. We also studied the first hyperpolarizability of the TDMImP and TPPS4 porphyrins, in the free-base form and in complex with Zn2+, Fe3+ and Mn3+. For TPPS4 we extended the study to observe the protonação effects in the free-base and the formation of oxo dimmers in FeTPPS4 complexes. The comparison between results from different compounds is hindered in most cases by different contributions from resonance enhancement. However, it was possible to verify that the presence of micelles has the effect of reducing the value of on H2TPPS4 pH 7. The HRS measurements in acid environment (pH 4) corroborates with the literature, indicating that desprotonation occurs in the presence of CTAB micelles. A theoretical and experimental study of three aminofenol isomers allowed to verify the effects of the relative positions of radical groups and the conjugation length on the first hyperpolarizability. The results show that in this case the change in the donor/acceptor character for different positions of the radical groups is more important than the increase in one unit in the conjugation length. We also studied compounds with the salen ligant, observing the effects of different lateral groups (ethane and DR1) and different complexes (H2, Cu2+, Ni2+ and VO2+) on the value of . It was possible to verify that, differently than the linear absorption the two-photon cross section, the compounds with DR1 shows an increase in the first hyperpolarizability that is much larger than the sum of the individual contributions of DR1 groups. The metal complexes have larger first hyperpolarizabilities than the ligant and the enhancement produced by different complexes follows the same pattern for both radical groups. Even after the strong increase in produced by the DR1 group, the much weaker effect of the complexes is preserved and measurable.

This research focuses on estimating the shear wave velocity (Vs) profile based on the dispersion curve obtained from SASW field test data (i.e., inversion of SASW data). It is common for the person performing the inversion to assume the prior information required to constrain the problem based on his/her own judgment. Additionally, the Vs profile is usually shown as unique without giving a range of possible solutions. For these reasons, this work focuses on: (i) studying the non-uniqueness of the solution to the inverse problem; (ii) implementing an inversion procedure that presents the estimated model parameters in a way that reflects their uncertainties; and (iii) evaluating tools that help choose the appropriate prior information. One global and one local search procedures were chosen to accomplish these purposes: a pure Monte Carlo method and the maximum likelihood method, respectively. The pure Monte Carlo method was chosen to study the non-uniqueness by looking at the range of acceptable solutions (i.e., Vs profiles) obtained with as few constraints as possible. The maximum likelihood method was chosen because it is a statistical approach, which enables us to estimate the uncertainties of the resulting model parameters and to apply tools such as the Bayesian criterion to help select the prior information objectively. The above inversion methods were implemented for synthetic data, which was produced with the same forward algorithm used during inversion. This implies that all uncertainties were caused by the nature of the SASW inversion problem (i.e., there were no uncertainties added by experimental errors in data collection, analysis of the data to create the dispersion curve, layered model to represent a real 3-D soil stratification, or wave propagation theory). At the end of the research, the maximum likelihood method of inversion and the tools for the selection of prior information were successfully used with real experimental data obtained in Memphis, Tennessee.

An effective way to describe changes in the microstructure of a material or to assess fatigue damage at an early stage in fatigue life is by measuring the acoustic nonlinearity parameter beta. The nonlinearity parameter is defined for harmonic longitudinal plane waves and it depends on the ratio of the amplitudes of the first harmonic of the exciting signal and the second harmonic. A reliable measurement of the amplitudes of these harmonics is crucial since their amplitude of the second (higher) harmonic is much smaller than the amplitude of the first harmonic. This research investigates the influence of the apparent nonlinearity that can occur due to the signal processing and shows how this influence can be quantified and minimized to enable a more accurate evaluation of the acoustic nonlinearity parameter. Furthermore the concept of the nonlinear parameter is extended to Rayleigh surface waves by developing a connection between the harmonic amplitudes and the third order elastic constants, using the approximate model by Zabolotskaya. Finally the problem of modeling the influence of fatigue damage on the nonlinear parameter and the elastic constants is discussed. The reduction of the processing nonlinearity combined with Rayleigh surface waves - Rayleigh surface waves are more efficient in the detection of fatigue damage initiated and concentrated at the surface - helps improve the prediction of fatigue damage and the remaining life of a sample.

Tez (Yüksek Lisans) - Süleyman Demirel Üniversitesi, Fen Bilimleri Enstitüsü, Jeofizik Mühendisliği Anabilim Dalı, 2008. / Kaynakça var.

Nonlinear mixing of two collinear, initially monochromatic, Rayleigh waves propagating in the same direction in an isotropic, nonlinear elastic solid is investigated: analytically, by finite element method simulations and experimentally. In the analytical part, it is shown that only collinear mixing in the same direction fulfills the phase matching condition based on Jones and Kobett 1963 for the resonant generation of the second harmonics, as well as the sum and difference frequency components caused by the interaction of the two fundamental waves. Next, a coupled system of ordinary differential equations is derived based on the Lagrange equations of the second kind for the varying amplitudes of the higher harmonic and combination frequency components of the fundamentals waves. Numerical results of the evolution of the amplitudes of these frequency components over the propagation distance are provided for different ratios of the fundamental wave frequencies. It is shown that the energy transfer is larger for higher frequencies, and that the oscillation of the energy between the different frequency components depends on the amplitudes and frequencies of the fundamental waves. Furthermore, it is illustrated that the horizontal velocity component forms a shock wave while the vertical velocity component forms a pulse in the case of low attenuation. This behavior is independent of the two fundamental frequencies and amplitudes that are mixed. The analytical model is then extended by implementing diffraction effects in the parabolic approximation. To be able to quantify the acoustic nonlinearity parameter, β, general relations based on the plane wave assumption are derived. With these relations a β is expressed, that is analog to the β for longitudinal waves, in terms of the second harmonics and the sum and the difference frequencies. As a next step, frequency and amplitude ratios of the fundamental frequencies are identified, which provide a maximum amplitude of one of the second harmonics as well as the sum or difference frequency components to enhance experimental results. Subsequently, the results of the analytical model are compared to those of finite element method simulations. Two dimensional simulations for small propagation distances gave similar results for analytical and finite element simulations. Consquently. this shows the validity of the analytical model for this setup. In order to demonstrate the feasibility of the mixing technique and of the models, experiments were conducted using a wedge transducer to excite mixed Rayleigh waves and an air-coupled transducer to detect the fundamentals, second harmonics and the sum frequency. Thus, these experiments yield more physical information compared to the case of using a single fundamental wave. Further experiments were conducted that confirm the modeled dependence on the amplitudes of the generated waves. In conclusion, the results of this research show that it is possible to measure the acoustic nonlinearity parameter β to quantify material damage by mixing Rayleigh waves on up to four ways.

L'instabilité de Rayleigh-Plateau est utilisée dans les dispositifs d'impression à jet continu (CIJ) afin de piloter la dynamique de brisure des jets d'encre. Son étude dans ce cas de figure s'inscrit dans un cadre pluridisciplinaire relevant de la mécanique des fluides, de la rhéologie, ou encore de la physique des polymères. Le travail effectué se focalise sur l'influence des propriétés du fluide ainsi que de la géométrie de la buse d'impression sur cette dynamique. Ainsi, la caractérisation expérimentale des propriétés physicochimiques et rhéométriques des encres fait l'objet d'une attention particulière. La dynamique de brisure est ensuite modélisée à l'aide de différents logiciels de simulation numérique puis comparée aux expériences effectuées par ailleurs. Ces simulations prennent en compte lorsque c'est le cas les comportements non newtoniens des encres étudiées telles que leur propriétés rhéofluidifiantes ou viscoélastiques. Un lien étroit entre la dynamique de brisure et la forme du profil de vitesse en sortie de la buse est mis en évidence. Ce lien semble constituer une piste d'investigation particulièrement intéressante dans le cadre de la prédiction des dynamiques de jets obtenues par les dispositifs d'impression industriels. / Rayleigh-Plateau instability is used in continuous ink jet (CIJ) printers in order to drive ink jets breakup. Studies of such mechanisms are based on pluri-disciplinary concepts dealing with fluid mechanics, rheology and polymer sciences. The present work focuses on fluid properties and nozzles designs influences onto breakup dynamics. In this context, the experimental characterization of ink physical and rheological properties are of particular interest. Thereafter, jet dynamics computations are performed using several software and compared with experiences. Potential non Newtonian behaviours such as shear-thinning or viscoelasticity are modelled by computations. A close link between breakup dynamics and velocity profile at the nozzle exit is highlighted. This link is believed to bring crucial information for the prediction of jet dynamics observed in industrial printers.

Les effets non linéaires de l’acoustique et en particulier le streaming de Rayleigh sont étudiés depuis les années 1850 où Lord Rayleigh fit l’observation d’un écoulement quasi permanent se superposant à l’onde acoustique qui se propageait dans un résonateur. Ce phénomène n’est donc pas nouveau et il a par ailleurs été le sujet de nombreuses études. Il a néanmoins été adopté comme point de départ de cette thèse, à ceci près que nous avons choisi de l’appliquer ici au cas particulier de la thermoacoustique. Cette nouvelle discipline qui a commencé à se développer dans les années 1980 met en œuvre un processus (basé sur la conversion réciproque entre énergie acoustique et énergie thermique) utilisé dans les systèmes thermoacoustiques tels que les moteurs ou réfrigérateurs. C’est une nouvelle technologie propre et fiable qui a de nombreux avantages. Cependant lorsque ces machines fonctionnent à forts niveaux acoustiques des effets indésirables viennent perturber le fonctionnement et réduire le rendement. Au cours de cette thèse nous nous sommes efforcés à analyser et évaluer expérimentalement ces effets indésirables et non linéaires qui se caractérisent entre autres par l’apparition du streaming de Rayleigh. Un objectif pas si élémentaire car ces phénomènes du second ordre amènent généralement à des situations délicates où les interactions et couplages entre les différents effets rencontrés sont très présents. L’interaction d’un gradient de température au sein du résonateur, de la géométrie de ce dernier ou encore l’interaction d’un stack thermoacoustique sur le streaming de Rayleigh sont autant de points sur lesquels nous nous sommes concentrés. Pour mener à terme cette étude, un premier résonateur acoustique muni d’une cellule de mesure a été utilisé pour valider la méthode expérimentale retenue. La PIV (Velocimétrie par Image de Particules) a été retenue comme technique la plus appropriée à la mesure des non linéarités de l’écoulement et du streaming de Rayleigh. Un second résonateur a ensuite été réalisé puis mis en place au laboratoire afin d’effectuer des mesures de plus grande envergure. Les résultats confirment les conclusions tirées de précédentes études et montrent la présence de quatre cellules contrarotatives au sein du résonateur. Par ailleurs la totalité du résonateur a pu être cartographiée permettant ainsi de visualiser l’ensemble des écoulements secondaires présents. L’intrication du streaming avec la température se révèle complexe. L’introduction de nouveaux éléments dans le résonateur (tels que les échangeurs) vient en effet créer des phénomènes qui se superposent aux effets déjà présents. Afin de continuer le travail débuté au cours de cette thèse, de nouveaux essais sont prévus. Ils permettront d’analyser plus finement les diverses interactions entre phénomènes. / Nonlinear acoustic effects and Rayleigh streaming in particular are studied since the 1850s when Lord Rayleigh made the observation of a quasi-steady flow superimposed on the acoustic wave propagating in a resonator. This phenomenon may not be new and it has moreover been the subject of numerous studies. However, it was adopted as the starting point of this thesis, except that we have chosen to apply it to the particular case of thermoacoustics. This new discipline that has started raising interest in the 1980s features a process –based on reverse conversion between thermal and acoustic energy- used in systems such as thermoacoustic engines and refrigerators. This is a new, clean and reliable technology that has many advantages. However, when these machines operate at high acoustic levels unwanted and nonlinear effects appear reducing the machine performances. In this thesis we therefore have tried to analyze and experimentally evaluate these effects which among other things are characterized by the appearance of Rayleigh streaming. This goal is not so elementary as these second-order phenomena generally lead to tricky situations where interactions and couplings between the different effects encountered are very present. The interaction of a temperature gradient within the resonator, the geometry of the latter or the interaction of a thermoacoustic stack on Rayleigh streaming are many points on which we focused. To complete this study, an acoustic resonator with a measurement cell was first used to validate the experimental method chosen. PIV (Particle Image Velocimetry) has proven to be an appropriate technique for the measurement of acoustical nonlinearities and Rayleigh streaming. A second resonator was then achieved and implemented in the laboratory to make measurements on a larger scale. The results confirm the findings of previous studies and show the presence of two counter-rotating cells within the resonator. Moreover the entire resonator has been mapped allowing visualizing all secondary flows. The interaction of streaming with temperature is complex. The introduction of new elements in the resonator such as heat exchangers has indeed created additional phenomena that superimposed on already existing effects. To continue the work started in this thesis, further tests are planned. They will further analyze the interactions between theses various phenomena.

Nesta tese apresentamos uma extensão da técnica de espalhamento hiper-Rayleigh (HRS) e sua aplicação para o estudo dos mecanismos que interferem na primeira hiperpolarizabilidade molecular (). Utilizamos um laser Nd:YAG, Q-switched e mode-locked como bombeio para excitar as amostras. Este laser emite pulsos de 100 ps modulados por uma envoltória de Q-switch. A saída é uma seqüência de pulsos com intensidades que acompanham a forma da envoltória. Usamos este trem de pulsos para excitar as amostras na medida de espalhamento hiper-Rayleigh, e um sistema de detecção com resolução temporal suficiente para resolver cada pulso independentemente. Esta modalidade de bombeio permitiu eliminar o controle mecânico da intensidade, o que reduziu o tempo necessário para a medida e melhorou a estabilidade nas condições experimentais. O método com trem de pulsos proporciona meios de identificar contribuições luminescentes e evitar valores superestimados para a primeira hiperpolarizabilidade. Realizamos testes medindo a molécula de paranitroanilina em vários solventes e verificamos muito boa reprodutibilidade dos valores da literatura. Comparamos os resultados medidos com valores calculados a partir do método de Hartree-Fock e corrigimos o engrandecimento por ressonância utilizando um modelo de dois níveis. A comparação entre valores teóricos e experimentais teve uma diferença média de 15%. Um estudo análogo para a molécula de dianilina não reproduziu os valores experimentais e atribuímos a falha à inaplicabilidade do modelo de dois níveis para medidas no regime ressonante. Também estudamos a primeira hiperpolarizabilidade nas porfirinas TDMImP e TPPS4, sob a forma base livre e formando complexos com Zn2+, Fe3+ e Mn3+. Para a TPPS4 estendemos o estudo para observar os efeitos da protonação na base livre e da formação de oxo dímeros na FeTPPS4 e as alterações causadas pela presença de micelas de CTAB. A comparação direta entre os resultados é dificultada em muitos casos pela diferença no engrandecimento por ressonância. Foi possível verificar que a presença de micelas tem o efeito de diminuir o valor de na H2TPPS4 pH 7. As medidas de HRS em ambiente ácido (pH 4) corroboram com a literatura, indicando que a ocorre desprotonação na presença de micelas. Um estudo teórico e experimental dos três isômeros do aminofenol permitiu analisar os efeitos da posição relativa dos grupos radicais e do comprimento da conjugação sobre a primeira hiperpolarizabilidade. Verificamos que a alteração no caráter doador/aceitador para diferentes posições dos grupos radicais tem influência maior no valor de do que o comprimento da conjugação. Utilizamos compostos com o ligante salen, com grupos laterais etano e DR1 e com ligantes H2, Cu2+, Ni2+ e VO2+, para estudar como os diferentes grupos e complexos refletem diferenças no valor de . Foi possível verificar que diferentemente da absorção linear e da seção de choque para dois fótons, o ligante com grupos radicais DR1 causam um aumento na primeira hiperpolarizabilidade que é muito maior do que a soma das contribuições individuais. Os complexos têm primeiras hiperpolarizabilidades maiores do que o ligante com H2 e a comparação entre os dois grupos com diferentes radicais mostra que existe uma correlação entre os aumentos causados por diferentes complexos. / This thesis reports an extension of the Hyper-Rayleigh scattering technique (HRS) and its application to study the mechanisms that contribute to the molecular first hyperpolarizabilities (). We use a Nd:YAG laser, Q-switched and mode-locked, as pumping beam to excite the samples. The laser delivers 100 ps pulses modulated by a Q-switch envelope, and the output is a pulse sequence which intensities follow the shape of the envelope. This pulse train is used to excite the samples in a Hyper-Rayleigh scattering experiment and the signal for each mode-lock pulse is detected independently. This modality of pumping allows the removal of the mechanical intensity control, therefore reducing measurement time and improved experimental stability. The method with pulse train also provides means to identify luminescent contributions and avoid overestimated values for the first hyperpolarizability. We performed test measurements with para-nitroaniline in several solvents and verified very good reproducibility of literature values. We also compared the measured and calculated values, obtained with the Hartree-Fock method and corrected for resonance enhancement with a two level model. The comparison between theoretical and experimental values results in an average difference of 15%. Similar studies for the dianiline molecule failed to reproduce experimental values and we attributed the failure to the inadequacy of the of the two-level model to correct resonance enhancement. We also studied the first hyperpolarizability of the TDMImP and TPPS4 porphyrins, in the free-base form and in complex with Zn2+, Fe3+ and Mn3+. For TPPS4 we extended the study to observe the protonação effects in the free-base and the formation of oxo dimmers in FeTPPS4 complexes. The comparison between results from different compounds is hindered in most cases by different contributions from resonance enhancement. However, it was possible to verify that the presence of micelles has the effect of reducing the value of on H2TPPS4 pH 7. The HRS measurements in acid environment (pH 4) corroborates with the literature, indicating that desprotonation occurs in the presence of CTAB micelles. A theoretical and experimental study of three aminofenol isomers allowed to verify the effects of the relative positions of radical groups and the conjugation length on the first hyperpolarizability. The results show that in this case the change in the donor/acceptor character for different positions of the radical groups is more important than the increase in one unit in the conjugation length. We also studied compounds with the salen ligant, observing the effects of different lateral groups (ethane and DR1) and different complexes (H2, Cu2+, Ni2+ and VO2+) on the value of . It was possible to verify that, differently than the linear absorption the two-photon cross section, the compounds with DR1 shows an increase in the first hyperpolarizability that is much larger than the sum of the individual contributions of DR1 groups. The metal complexes have larger first hyperpolarizabilities than the ligant and the enhancement produced by different complexes follows the same pattern for both radical groups. Even after the strong increase in produced by the DR1 group, the much weaker effect of the complexes is preserved and measurable.