The photochemistry of several novel photoacids was addressed experimentally and theorectically. Initial studies focused on the excited-state proton transfer (ESPT) of several chiral phtoacids and explored the effects of chirality on ESPT; subsequent studies examined photochemistry and photophysics of "super" photoacid N-methyl-6-hydroxyquinolinium (MHQ). In the initial studies, no enantioselectivity was observed from the chiral photoacids to various chiral proton acceptors. In the later studies examining ESPT in MHQ both experimentally and theoretically, the excited-state acidity constant of the photoacid was determined to be an unprecedented -7, making it the strongest photoacid reported in the literature to-date. Consideration was then given to applications of the novel photoacid including its properties as a photoinitiator in cationic polymerizations and as a photochemical probe in gas-expanded liquids and in the Nafion membrane. In the course of these studies, an interesting fluorescence quenching effect was observed that became the subject of some exploratory studies that suggest a nucleophilic quenching mechanism.

In this thesis we describe the development of a real-space implementation of the Bethe-Salpeter equation (BSE) and use it in conjunction with a semi-empirical tight-binding model to investigate the optoelectronic properties of colloidal quantum- confined nanostructures. This novel implementation exploits the limited radial extent and small size of the atomic orbital basis to treat finite systems containing up to ∼4000 atoms in a fully many-body framework. In the first part of this thesis our tight-binding model is initially benchmarked on zincblende CdSe nanocrystals, before subsequently being used to investigate the electronic states of zincblende CdSe nanoplatelets as a function of thickness. The band-edge electronic states are found to show minimal variation for a range of thicknesses and the results of our tight-binding model show good agreement with those predicted using a 14-band k·p model for a nanoplatelet of 4 monolayers (ML) in thickness. Optical absorption spectra were also computed in the independent-particle approximation. While the results of the tight-binding model show good agreement with those of the 14-band k·p model in the low-energy region of the spectrum, agreement with experiment was poor. This reflects the need for a many-body treatment of optical absorption in nanoplatelet systems. In the second part of this thesis we apply our tight-binding plus BSE model to study the excitonic properties of CdSe nanocrystals and nanoplatelets. Simulations performed on CdSe nanocrystals examined an approximation of the BSE equivalent to configuration interaction singles (CIS), and found that both the optical gap and the low-energy spectral features were unaffected by the approximation. A comparison of exciton binding energies with those predicted by CIS demonstrates the sensitivity of results to the exact treatment of dielectric screening and the decision of whether or not to screen exchange. Our model predicts optical gaps that are in strong agreement with average experimental data for all but the smallest diameters, but was not able to reproduce low-energy spectral features that were fully consistent with experiment. This was attributed to the absence of the spin-orbit interaction in the model. Simulations performed on CdSe nanoplatelets investigate the optical gaps and exciton binding energies as a function of thickness. Exciton binding energies were found to reach ∼200 meV for the thinnest system, however, optical gaps were slightly overestimated in comparison to experiment. This is attributed to the reduced lateral dimensions used in our simulations and our bulk treatment of dielectric screening. A two-dimensional treatment of dielectric screening is expected to further increase binding energies. Calculations of the excitonic absorption spectrum reproduce the characteristic spectral features observed in experiment, and show strong agreement with the spectra of nanoplatelets, with thicknesses ranging from 3 ML to 5 ML.

Pluronics are triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) available in different molecular weights and PPO/PEO ratios. Pluronic hydrogels are able to dissolve hydrophobic compounds and they have application in different areas including drug delivery systems and oil recovery. The structure of Pluronic polymers can be designed for specific application by changing the size and ratio of the PPO and PEO blocks. In aqueous environments, the PPO blocks of different unimers form aggregates as they are more hydrophobic compared to the PEO blocks, and in the aggregates the PPOs have less exposure to water. The PEO blocks that are still hydrophilic remain soluble in water and form a shell around the PPO aggregated core. Moreover, some of the Pluronic copolymer aqueous solutions can form hydrogels at elevated temperatures. The aim of this thesis is to study the microheterogeneity of two different Pluronic hydrogels using singlet excited state probes and also study the mobility of small molecules in Pluronic hydrogels using triplet excited state probes. In the first project, the properties of different microenvironments in Pluronic F127 (PEO99PPO65PEO99) were characterized. The quenching of singlet excited state probes was used to determine the number and characteristics of solubilization sites in F127 hydrogels. This method was used to gain information on the accessibility of different quenchers to singlet excited molecules bound to the micellar structures. Singlet excited states are short lived, and these excited states do not move within the gel before their decay to the ground state. The techniques used for these studies were steady-state fluorescence and time-resolved fluorescence spectroscopies. My results showed that there are different solubilization sites in F127 micelles and the accessibility of quenchers to the singlet excited molecules bound to the micellar structure depends on the nature of the quencher and the size of the excited molecules. In the second project, the different microenvironments in Pluronic P104 (PEO27PPO61PEO27) were characterized, and these results were compared with those obtained for the Pluronic F127. Pluronic P104 has similar units of PPO blocks as F127 but different units of PEO blocks which results in different properties between these two Pluronic copolymers. My results showed that the solubilization sites inside Pluronic micelles changes with the change in PEO/PPO ratio. In the third project, I studied the mobility of different small molecules between aqueous and micellar environments in the F127 hydrogel by quenching triplet excited state probes. Excited triplet states are suitable for such studies because their lifetimes are longer than the lifetimes for singlet excited states. The laser flash photolysis technique was used for this aim. The results showed that the exit from the micellar environment is slow and depend on the size and hydrophobicity of the probe molecules. / Graduate / 2022-05-11

Photovoltaic (PV) technologies could provide abundant, clean and secure energy through the conversion of sunlight into electricity, but currently are too expensive to compete with conventional sources of power. Novel PV devices incorporating nanostructured materials, such as the dye-sensitized solar cell (DSC), have been identified as viable, low-cost alternatives to traditional solar cell designs. In spite of technological progress in the field over the last twenty years, the underlying physics governing DSC operation is still not well understood. In this thesis, first-principles (i.e. parameter-free) calculations are performed with the aim of connecting experimentally-measured photoemission data to the underlying atomistic and electronic structure of interfaces found in DSCs. The principal system under study is the interface between anatase titanium dioxide (TiO₂) and the "N3" dye molecule, one of the most widely-investigated device designs in DSC research. Atomistic models of the interface are determined within density-functional theory. Core-level spectra of these interface models are then calculated using a ∆SCF approach. Comparison of the calculations to published experimental data finds that intermolecular interactions have a significant effect on the spectra. Next, the electronic structure of bulk TiO₂ and of isolated N3 molecules is calculated using the GW approximation and ∆SCF method respectively. For the former, it is shown that including Hubbard U corrections in the initial Hamiltonian reduces the GW gap by 0.4 eV. These calculations are then used to determine the valence photoemission spectrum of the full interface. By including image-charge effects, thermal broadening and configurational disorder, quantitative agreement with experimentally-measured spectra is demonstrated. In addition to the N3/TiO₂ system, calculations of the core-level spectra of the interfaces between TiO₂ and H₂O and bi-isonicotinic acid are also presented. The thesis concludes with a study of the X₂Y₃/TiO₂ interfaces (X=Sb, Bi; Y=S, Se) found in recently-developed semiconductor-sensitized solar cells.

No description available.

A experiência E781/SELEX acumulou um total de 1 bilhão de eventos de trígger charmoso em fita utilizando um feixe secundário de POT.-/ POT.- de 600 GeV/c e um de próton de 500 GeV/c, ambos a partir do feixe de prótons de 800 GeV/c gerado pelo Tevatron no Fermilab. Aqueles incidiram em alvos de cobre e carbono com o objetivo de estudar a produção e o decaimento de estados charmosos. Neste trabalho estudamos os estados POT. ++0 IND.C(2455) c++/- e POT. ++0* IND.C (2520) POT.+ IND. C POT. +/- a partir dos dados da E781 tomados durante o período de Dezembro de 1996 até Setembro de 1997. Obtivemos as medidas de massa e largura para dos báríons IND.C e * IND.C com valores: M IND. c++ M IND. c+ = 167.5 ± 0.5 ± 0.2MeV/c2, M IND. c POT.0 -- M IND. c+ = 167.9 ± 0.7 ± 1.2 MeV/c2, M IND. c++* M IND. c+ = 237.4 ± 4.9 ± 3.1MeV/c2, M IND. c POT.0* -- M IND. c+ = 232.6 ± 1.7 ± 1.3 MeV/c2, M IND. c++- = 16.2 ± 7.8 ± 5.5MeV e M IND. c POT.0* = 9.1 ± 6.0 ± 6.2MeV. Fizemos também o estudo de hadroprodução destes estados medindo o parâmetro que caracteriza a distribuição em x IND.f. OS valores obtidos são: n IND. c++ = 2.57 ± 0.57 ± 0,45, n IND. c POT.0 = 1.37 ± 0,27 ± 0.43, n IND. c++ = 2,13 ± 0,26 ± 0,61, n IND. c POT.0- =2.05 ± 0,35 ± 0,80. / The experiment E781/SELEX collected a total of 1 billion charm trígger events ou tape using a 600 GeV/c -/ and a 500 GeV/c proton secondary beams, both from the 800 GeV/c proton beam delivered by the Fermilab Tevatron, Those beams reached the copper and carbon targets. The main goal was to study charm hadron production and decays. This work is dedicated to study the c++/0(2455) c++/- e c (++/0)*(2520) c++/- states from the E781 data obtained from December 1996 to September 1997. We obtained the mass and width values for the c and c* bárions as: M c++ M c+ = 167.5 ± 0.5 ± 0.2MeV/c2, M c0 -- M c+ = 167.9 ± 0.7 ± 1.2 MeV/c2, M c++* M c+ = 237.4 ± 4.9 ± 3.1MeV/c2, M c0* -- M c+ = 232.6 ± 1.7 ± 1.3 MeV/c2, M c++- = 16.2 ± 7.8 ± 5.5MeV e M c0* = 9.1 ± 6.0 ± 6.2MeV. We also studied the hadroproduction for those states measuring the paramenter that characterizes the xf distribution. The values obtained are: n c++ = 2.57 ± 0.57 ± 0,45, n c0 = 1.37 ± 0,27 ± 0.43, n c++- = 2,13 ± 0,26 ± 0,61, n c0- =2.05 ± 0,35 ± 0,80.

La théorie de la fonctionnelle de la densité dépendante du temps (TDDFT) est une méthode basée sur la densité pour calculer les états excités. Bien que la TDDFT soit une théorie exacte, on doit en pratique partir d'une approximation de la fonctionnelle d'échange-corrélation, qui reste inconnue. L'approximation adiabatique est l'approximation de la fonctionnelle la plus courante. Cette approximation donne de très bons résultats pour les propriétés spectroscopiques, mais elle est inexacte pour les simulations en photochimie. Dans cette thèse, on montre que l'origine du problème réside dans l'approximation de la fonctionnelle de corrélation. Le résultat principal de la thèse consiste en un noyau de corrélation, qui peut être utilisé dans la formulation de la réponse linéaire, noyau dérivée à partir de la théorie des perturbations à plusieurs corps. Le noyau inclut de façon générale les excitations doubles qui donnent l'effet principal à la corrélation dans les états excités. La comparaison de ce noyau avec la fonctionnelle adiabatique nous a permis d'identifier les termes manquants à ce dernier. Nous avons testé la possibilité d'ajouter ces termes comme une correction à l'approximation adiabatique. Le noyau pourrait potentiellement être appliqué à des systèmes de grosse taille. / Time-dependent density-functional theory (TDDFT) is a density-functional method for calculating excited states. TDDFT is formally exact, though in practice one has to approximate the unknown exchange-correlation functional, which contains all the unknown many-body effects. The adiabatic functionals are the most commonly used. Although they are very successful for spectroscopy, the adiabatic functionals are too inaccurate to be applied to photochemistry. In this thesis, we show that the main problem is due to the approximations in the correlation functional. The main result of the thesis is a correlation kernel for linear-response TDDFT, derived using many-body perturbation theory techniques, which generally includes double excitations, thus introducing the leading correlation effects in the excited states. The comparison of this kernel with the adiabatic functionals allowed us to identify which correlation effects are missing in these approximation. We tested the possibility of improving the description of correlation by adding the missing terms from many-body theory to the adiabatic functionals. This mixed kernel is more efficient than the full many-body kernel, and can potentially be applied to systems of medium to large size.

Density functional theory is used to calculate the core excitation spectra of titanium structures. Specifically, the core-hole approximation is used. In this scenario, the excitation energies of core electrons are calculated using the approximation that the core energy level be frozen throughout the relaxation process of the orbitals. This allows a more acurate determination of the resulting X-ray spectra. The method described has been implemented in an NWChem module.

No description available.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 115-124).