Both of dianhydride and diamines are made to synthesize second-order nonlinear optical polyimides containing side-chained benzobisthiazole based chromophores by method of chemical cycle. Then, this study regarded high Tg and high thermal stability of polyimides as main-chain of polymers and this study regarded high dipolemoment of chromophores as side-chain of polymers Finally, combine two parts into two kind of nonlinear optical polyimides. By changing the structure of main-chain and side-chain, chromophore poled can reduce space-hinder and enhance the electrooptical coefficient r33. This study can identify functional group, the larger absorption wavelength and dissocation temperature of structure of nonlinear optical polyimides by instruments of IR, UV, TGA,¡Ketc. In the measurement of nonlinear optics, polymers owning both of larger dipoleminents and -ether group are regularly poled in characterisitc orientation. Therefore, these polymers have a higher electrooptical coefficient r33. In this results, the r33 of NLO-PIB film is 7.70 pm/V and the r33 of NLO-PIB film is 7.64 pm/V at room temperature.

In this study, we extend the rigidity and resonance of benzobisthiazole for the application as second-order nonlinear optics. A novel nonlinear optical polyimide (NLO-PI) containing side-chained benzobisthiazole- based chromophore has been synthesized. A hydroxyl- containing PI (W2) was prepared using direct thermal imidization of 4,4'-diamino-4"- hydroxytriphenylmethane(DHTM) and 4,4¡¦-(hexafluoroisopropylidene) diphthalic anhydride; the benzobisthiazole-based chromophore was then prepared using 2,5-diamino-1,4- benzenedithiol dihydrochloride as the starting monomer. The final NLO-PI was obtained by the Mitsunobu reaction via ether linkage between W2 and the chromophores. This ether linkage is expected to provide chain flexibility for better orientation under electric field during poling. The C=C bonds inside the chromophores also provide more orientation probabilities and conjugation length. Formation of benzobisthiazole-based chromophore and the corresponding NLO-PI was evidenced by FTIR and UV-vis spectra. TGA reveal a thermal decomposition temperature as high as 350oC, respectively. The electrooptic coefficient of the NLO-PI at a wavelength of 830nm was found to be r33=9.75 pm/V.

Based on a series of study to improve the electrooptic coefficient (r33) of nonlinear optical polyimides (NLO-PI) containing benzobisthiazole- based chromophores in our lab, this work concentrated on the modification of the benzobisthiazole-based chromophore VIII (r33 = 6.62 pm/V). At first, a hydroxyl-containing polyimide was first synthesized by using dianhydride and diamine as reactants via thermal imidization and the benzobisthiazole-based chromophores were synthesized by using DABDT as the starting monomer. The NLO precursors were obtained by the Mitsunobu reaction via ether linkage between PI and chromophore; it was then cured at 300¢J to result in the final NLO-PI. The benzobisthiazole-based chromophore of VIII was modified with an insertion of the ethoxy group between the NLO moiety and the main PI backbone to get the NLO-V-1. This method makes the chromophore easier to orient under the electric field during poling; thus a higher r33 (7.4 pm/V) is ensured. NLO-V-2 is another modified sample which had a phenyldiazene group inserted into the chromophore of VIII to increase the conjugated length; this results in a red shifts from 390 nm (VIII) to 484 nm in UV-abs spectrum but the r33 (5.8 pm/V) has only a slight improvement.

This thesis is sub-divided into two parts. Part (i) is entitled 'Structure / Property Relationships in Non-linear Optical Materials' (chapters 1-8) whilst part (ii) is entitled 'Structural Studies of imido, (bis)imido and aryloxide group VA and VIA transition metal complexes' (chapters 9-10).Chapters 1, 2 and 3 provide an introduction to non-linear optics, X-ray and neutron experimental techniques used in this thesis and charge density studies respectively. Chapters 4 to 8 describe the investigations of the part (i) topic. These include bond length alternation studies on a series of tetracyanoquinodimethane derivatives and a charge density study of one of these compounds in chapter 4. Several other charge density studies are reported in chapters 5 and 6 which concentrate on methyl- nitropyridine and nitroaniline derivatives and the compound, 3-( 1,1 -dicyanoethenyl)-l-phenyl-4,5- dihydro-1 H-pyrazole (DCNP) respectively. Chapter 5 also deals with the effect of intermolecular interactions on the non-linear optical phenomenon whilst in chapter 6, a detailed analysis of the thermal motion present in DCNP is also given. Investigations on intermolecular interactions are also reported in chapters 7 and 8 which studies the compounds, N-methylurea and zinc(tris)thiourea sulphate respectively. In the former case, the neutron derived structure of N-methylurea is reported at two temperatures and it is revealed that disorder is present at the higher temperature. In the latter case, neutron results from an instrument presently in the testing stages of its development are reported and contrasted with those obtained using a well established instrument. Chapters 9 and 10 describe the investigations of the part (ii) topic. These concentrate on the structural features of two series of organometallic compounds which have potential use as polymerization catalysts. Relationships between structure and reactivity are reported.

In this thesis I will introduce a novel nonlinear optical microscopy method to address some of the shortcomings in the current nonlinear optical microscopy literature and offer a supplement to traditional fluorescent microscopy for label free optical biomedical imaging. In order to demonstrate this method I describe a method for the generation of a numerical sample of collagen fibrils, produce a set of numerical diffraction measurements. I introduce a novel Ptychography model for the simultaneous reconstruction of the components of the nonlinear optical susceptibility tensor and demonstrate the results of this model using numerically generated measurements from a numerical collagen sample. I additionally use the recovered information from Ptychography to retrieve new information about the structure of a sample.

This thesis describes the computational tools that allow the simulation of polymers made up of an arbitrary number of three-level systems, the study of such systems and comparisons to experimental nonlinear optical spectra. The three-level system generator (3LSG), is designed to automatically generate the operators that describe the system, whether it is a closed system or an open quantum system (OQS) in contact with a bath, with just a few input parameters. A user is free to specify each 3LS's energy levels and transition dipoles between said levels, site couplings between the different units of the polymer and in the case of open systems, the rates and couplings describing the different relaxation processes taking place in an OQS, using the Redfield formalism. In either cases, the 3LSG is then capable of generating the Hamiltonian 𝐻₀ describing the closed system or the Liouvillian 𝓛₀ describing the open system from the various inputs. The Ultrafast Spectroscopy Suite (UFSS) is an open-source software suite used to perform the nonlinear optical spectroscopies simulations. It contains 4 main modules, one of which is the Hamiltonian/Liouvillian Generator (HLG), a module previously designed to model simpler two-level systems. The 3LSG is a sub-module of the HLG. The three-level system generator is used to replicate a theoretical model describing a copolymer model made of many identical pairs of squaraine monomers, where each monomer is a three-level system interacting with its neighbouring sites and a surrounding bath. The system automatically generated by the 3LSG is used, along with other spectroscopic calculation tools, to simulate high-order transient absorption (TA) spectroscopies and study the long-time behaviour of the 3rd-order to 13th-order excited state absorption (ESA) peaks in the TA signals. The 3LSG is used in conjunction with spectroscopic calculations tools as it was originally intented, though it may also be used by itself to study Hamiltonians and Liouvillians of electronic three-level systems.

Some basic concepts and principles of optical dielectric slab waveguiding and experimental methodology involving characterisation of waveguide films are introduced, Results from the characterisation of thin polymeric waveguide films and measurements of refractive indices of the films are presented. The birefringence of some polymer films is analysed and discussed. The photostabilities of several dopants (DEMI, Ultra-DEMI, Dicyclohexyl-DEMI, Mor2, Morpip and DCM) are investigated in a polymer matrix (PMMA), and their measured photostabilities are presented. These organic chromophores change their properties in the course of photodegradation. Degradation experiments are carried out by exposing the doped waveguide films to light in air, vacuum and nitrogen environments. The degradation mechanisms of these chromophores are discussed. It is found that the degradation of the DEMI, Ultra-DEMI, Dicyclohexyl-DEMI and DCM are due to photooxidation, their photostabilities are much higher in vacuum than in air. The Mor2 and Morpip degrade by direct photodecomposition, their photostabilities are in the same order when exposed to light in their main absorption bands. The oxygen free environment (e.g. vacuum) is essential to increase their photostabilities. A beam branching effect in DCM doped waveguide film is observed. Stacked multi-layer waveguides are investigated as possible humidity sensors. Symmetric structure (PMMA/P-4VP/PMMA/P-4VP/PMMA) (P4VP-I) and unsymmetric structure (Si02/P-4VP/Zeonex/P-4VP/Air) (P4VP-II) are studied. Special procedures and process have been developed to fabricate multi-layer waveguide structures in experiments. It is found that both structures have good reversibilities and show reasonable stabilities. 30 ppm concentrations of water vapour can be detected by the P4VP-II structure. The experimental results show that the overall response of P4VP-II structure exhibits good linearity with increase of the concentration of water vapour. The structures can not only measure the phase shift of interference, but also can measure the direction of fringe movement. The sensitivity of the structure can be further improved by using different combinations of polymers in the structure.

Plasmonic structures with nanometer scale gaps provide localized field enhancement and allow for engineering of the optical response, which is well described by conventional classical models. For subnanometer scale gaps, quantum effects and nonlocal effects become important and classical electromagnetics fail to describe the plasmonic coupling response. Coupled plasmonic system of gold nanoparticles on top of thin gold film separated with self-assembled monolayers (SAMs) provides a convenient geometry to experimentally explore plasmonic features in subnanometer scale gaps. However, the surface roughness of the thin metal film can significantly influence the plasmonic coupling properties. In this dissertation, I suggest modifying the coupled nanoparticles-film structures by using ultraflat thin metal films. Using these structures, I investigated the far-field optical response for gap size variations by dark field scattering measurements. A red-shift of the plasmon resonance wavelength was observed by reducing the gap width. However, I did not observe the previously reported saturation trend of the resonance shift for subnanometer scale gaps. I attribute the difference to surface roughness effects in past works since as they were not present in my studies with ultraflat films. To study the near-field enhancement in subnanometer scale gaps, I used third harmonic generation as a method that is highly sensitive (as the third power) to the local field intensity. The onset of the quantum tunneling regime was determined for gap thicknesses of 0.51 nm, where there was a sudden drop in the third harmonic when the gap width decreases from 0.69 nm to 0.51 nm. The experimental observations were consistent with analytical calculations that applied the quantum-corrected model for SAM separating two gold regions. In comparison to the gap without SAMs in which the onset of the tunneling regime was reported at 0.31 nm, the onset of tunneling across the gap with SAM occurred for larger gaps. This was an expected outcome because the material in the gap reduced the barrier height to tunneling. Furthermore, I investigated the wavelength dependence of the third harmonic generation for the gold plasmonic system to determine the role of the interband transitions in the nonlinear response of gold. Past works reported a strong wavelength dependence of the nonlinear response of gold for the fundamental wavelength at about 550 nm, attributed to the interband transitions between the 5d to 6s-6p bands. However, the roles of the interband transitions and wavelength-dependent field enhancement in the nonlinear response of gold was not investigated. In this dissertation, results showed the third harmonic generation enhanced by an order of magnitude by the interband transition (as compared to the non-resonant case). In my research I also used an analytic model for the dielectric function of gold in which contributions of the interband transitions were considered. This model was also consistent with the experimental observations. / Graduate / 0752 / 0544 / Ghazal.hajisalem@gmail.com

The leading cause of death in patients who survive subarachnoid hemorrhage (SAH) is stroke as a result of cerebral arterial vasospasm1. Such vasospasms involve a vasoactive response, but they remain enigmatic and no clinical treatment has proven effective in prevention or reduction2. Arteries remodel in response to diverse mechanical loads and chemical factors. Following SAH, the surrounding vasculature is exposed to a radically altered chemo-mechanical environment. It is our hypothesis that chemical stimuli associated with the formation of an extravascular blood clot dominates the maladaptive growth and remodeling response early on, thus leading to important structural changes. However, it is not clear which of the many chemical factors are key players in the production of vasospasm. Before an accurate picture of the etiology of vasospasm can be produced, it is imperative to gain a better understanding of the non-pathogenic cerebral vasculature. In particular, the rabbit basilar artery is a well established model for vasospasm. However, surprisingly little is known about the mechanical properties of the rabbit basilar artery. Using an in vitro custom organ culture and mechanical testing device, acute and cultured basilar arteries from male White New Zealand specific pathogen free rabbits underwent cyclic pressurization tests at in vivo conditions and controlled levels of myogenic tone. Sections of basilar arteries were imaged for collagen fiber orientation at 0, 40 and 80 mmHg at in vivo stretch conditions using nonlinear optical microscopy. The nonlinear stress-strain curves provide baseline characteristics for acute and short-term culture basilar arteries. The active and passive testing creates a framework for interpreting the basal tone of arteries in our culture system. Nonlinear optical microscopy second harmonic generation provides unique microstructural information and allows imaging of live, intact arteries while maintaining in vivo geometries and conditions. Collagen fibers were found to be widely distributed about the axial direction in the adventitial layer and narrowly distributed about the circumferential direction in the adventitial layer. The quantified collagen fiber angles within the artery wall further support the development of accurate mathematical models.

The leading cause of death in patients who survive subarachnoid hemorrhage (SAH) is stroke as a result of cerebral arterial vasospasm1. Such vasospasms involve a vasoactive response, but they remain enigmatic and no clinical treatment has proven effective in prevention or reduction2. Arteries remodel in response to diverse mechanical loads and chemical factors. Following SAH, the surrounding vasculature is exposed to a radically altered chemo-mechanical environment. It is our hypothesis that chemical stimuli associated with the formation of an extravascular blood clot dominates the maladaptive growth and remodeling response early on, thus leading to important structural changes. However, it is not clear which of the many chemical factors are key players in the production of vasospasm. Before an accurate picture of the etiology of vasospasm can be produced, it is imperative to gain a better understanding of the non-pathogenic cerebral vasculature. In particular, the rabbit basilar artery is a well established model for vasospasm. However, surprisingly little is known about the mechanical properties of the rabbit basilar artery. Using an in vitro custom organ culture and mechanical testing device, acute and cultured basilar arteries from male White New Zealand specific pathogen free rabbits underwent cyclic pressurization tests at in vivo conditions and controlled levels of myogenic tone. Sections of basilar arteries were imaged for collagen fiber orientation at 0, 40 and 80 mmHg at in vivo stretch conditions using nonlinear optical microscopy. The nonlinear stress-strain curves provide baseline characteristics for acute and short-term culture basilar arteries. The active and passive testing creates a framework for interpreting the basal tone of arteries in our culture system. Nonlinear optical microscopy second harmonic generation provides unique microstructural information and allows imaging of live, intact arteries while maintaining in vivo geometries and conditions. Collagen fibers were found to be widely distributed about the axial direction in the adventitial layer and narrowly distributed about the circumferential direction in the adventitial layer. The quantified collagen fiber angles within the artery wall further support the development of accurate mathematical models.